Special Mixing Behavior of Chelate-based Ionic Liquid with Methanol

Compared to the general ionic liquids (ILs), a significant deviation of the binary mixtures of 1-decyl-3-methylimidazolium tri(hexafluoroacetylaceto)-copper(II) ([C₁₀mim][Cu(hfacac)₃]) with methanol was found, indicating the way methanol interacts with ILs might be governed by the special structure of the chelating anion. IR results showed that the (C2-H) of 1-decyl-3-methylimidazolium hexafluoroacetylacetonate ([C₁₀mim][hfacac]) blue-shifted more significantly than that of [C₁₀mim][Cu(hfacac)₃], meanwhile the (C=O) red-shifted in [C₁₀mim][Cu(hfacac)₃], which is contrast with that in [C₁₀mim][hfacac]. Two-dimensional correlation analysis of the FTIR spectra indicated that the chelating cavity has little effect on the sequence of the ILs sites that interact with methanol. Combined with small angle X-ray scattering (SAXS) results, the picture of mixing processes in these two systems were proposed. Methanol interacts directly with the anion followed by the cation in [C₁₀mim][hfacac], while methanol preferentially enters the chelating cavity and enhances the packing effect in the [C₁₀mim][Cu(hfacac)₃] system.     

Free energies of transfer of alkali halides from water to urea-water mixtures at 25°C from EMF measurements

The standard potentials_s E ^o of M/M⁺ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values of_s E ^o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G _t ^o (MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li⁺ to Na⁺ but fall from Na⁺ to K⁺ and rather sharply from K⁺ to Cs⁺ with a maximum at Na⁺ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G _t ^o (i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions.     

Pervaporation separation of alkane/thiophene mixtures with PDMS membrane

Worldwide concerns over environment have stimulated increasing interest both in academic and industry for deep desulfurization of gasoline. Polydimethylsiloxane (PDMS) composite membrane was used to separate the binary and multicomponent alkane/thiophene mixtures by pervaporation. Effect of carbon number and concentration of alkane, and of feed temperature, on the separation efficiency of alkane/thiophene mixtures was investigated experimentally. Experimental results of binary mixtures indicated that the total fluxes for different alkane/thiophene mixtures decrease with increase of carbon number in the alkanes. Corresponding activation energies of permeation for alkanes in PDMS membrane increase with increase of carbon number in the alkanes. Differences of molecular size and structure of the alkanes lead to various selectivities thereof within PDMS membrane. In addition, the permeability and activation energy of thiophene in various systems differ from each other due to coupling effect which should be taken into consideration when dealing with multicomponent systems. Pervaporation results of ternary systems indicated that, the increase of content of lighter alkane in feed would result in a larger total flux, but a smaller selectivity to thiophene simultaneously. A quaternary system, the mixture of n-heptane, n-octane, n-nonane and thiophene, was employed to simulate the desulfurization process of gasoline. With the membrane having a PDMS layer of 11 μm, the total flux was measured to be about 1.65 kg/m² h, with the corresponding enrichment factor of thiophene 3.9 at 30 °C.     

Aspects of investigating scrambling in the synthesis of porphyrins: different analytical methods

Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture.     

聚合物 分散液晶体系的相分离结构对温度依赖性的研究

在不同温度下采用紫外光引发相分离法制备了聚合物分散液晶样品．用光学显微镜及扫描电镜研究了样品的相分离结构．采用对样品施加电压观察其微结构轮廓，或测量液晶微粒相变点的简单方法研究了聚合温度对相分离结果的影响．结果表明，在一定温度范围内，随着温度的增高，液晶微粒的平均尺寸趋于减小，而且形成的液晶微粒也逐渐变纯．作者给出了这些测试结果并进行了讨论．     

Adsorption of the Ternary Liquid Mixture Ethanol/n-Octane/n-Hexadecane onto Activated Carbon: I. The Adsorption Excess of the Ternary Mixture and of Its Binary Combinations

The adsorption isotherms of the binary mixtures of ethanol/n-Octane, ethanol/n-hexadecane and n-octane/n-hexadecane onto the activated carbon TA 95 were measured at 278 K, 288 K, 298 K and 308 K and described with mathematical functions. About 300 experimental values of the adsorption excess of the ternary mixture ethanol/n-octane/n-hexadecane onto activated carbon TA 95 at 298 K were measured by gas chromatography inside the ternary triangle. The ternary miscibility gap was determined at three temperatures. A good representation of the ternary data and the calculated activity coefficients (using the UNIFAC model) in three-dimensional space was possible with the help of transformation of coordinates. It was possible, too, by utilization of the conception of the quasi two-component representation of the mole fractions with and without miscibility gap. Several influencing factors on ternary adsorption isotherms were discussed for the system ethanol/n-octane/n-hexadecane/TA 95.     

Solute-solvent interactions in water-tert-butyl alcohol mixtures. VI. Enthalpies of solution for halo-para-substituted benzoates

Enthalpies of solution of sodium benzoate, potassium benzoate, and potassium halo-substituted benzoates are reported at 298.15°K in water and in nine water-tert-butyl alchol mixtures. Transfer enthalpies from water to the mixed solvent go through a maximum for about 0.055 mole fraction of alcohol. Additivity of ionic contributions in the enthalpies of transfer is verified. Substituent effects on the transfer enthalpies of benzoates are discussed in terms of size of the solutes and cohesion of the solvent mixtures. For Part V, see ref. 1.     

A NMR method for the analysis of mixtures of alkanes with different deuterium substitutions

¹³C NMR at 125.76 MHz with ¹H and ²H decoupling, ²H NMR at 76.77 MHz with ¹H decoupling, and ¹H NMR at 500.14 MHz with ²H decoupling were employed as analytical tools to study the complex mixtures of deuterated ethanes resulting from the catalytic H–D exchange of normal ethane with gas-phase deuterium in the presence of a platinum foil. Reference samples consisting of 1:1 binary mixtures of pure normal ethane and ethane-d_n (n=1–6) were used to identify the peak positions in the ¹³C, ²H, and ¹H NMR spectra due to each individual isotopomer, and the effect of isotopic substitution on the chemical shifts was determined in each case. While the NMR of all three nuclei worked well for the identification of the individual components of the 1:1 standard mixtures, both ¹H and ²H NMR suffered from inadequate resolution when studying complex reaction mixtures because of the broadening of the lines due to ¹H–¹H (¹H NMR) and ²H–²H (²H NMR) couplings. ¹³C NMR was therefore determined to be the method of choice for the quantitative analysis of the reaction mixtures. Using the ¹³C NMR results, a correlation that takes into account the primary and secondary isotope substitution effects on chemical shifts was deduced. This equation was used for the identification of the individual components of the mixtures, and integration of the individual observed resonances was then employed for quantification of their composition. This study shows that ¹³C NMR with ¹H and ²H decoupling is a viable procedure for studying mixtures of deuterated ethanes. Furthermore, the additivity of the isotopic effects on chemical shifts and the transferability of the values obtained with ethane to other molecules makes this approach general for the analysis of other isotopomer mixtures.     

Correlation of the volumes and heat capacities of solutions with their solid-liquid phase diagrams

Liquid systems which have strong non-idealities, as seen from their thermodynamic properties, often show evidence of these interactions in the solid-liquid phase diagrams. This suggests that some of the structures present in the solid state can persist in the solution state, on a time average, up to temperatures much higher than the melting point. Volumes and heat capacities of typical systems were either taken from the literature or measured to illustrate this correlation with the phase diagrams. With mixtures of aprotic solvents which show nearly-ideal simple eutectic phase diagrams, the properties of the solutions are also nearly ideal. Examples of systems investigated which show strong non-idealities are ionic surfactant solutions, alcohol-water mixtures, chloroform-triethylamine mixtures and lithium salts in aprotic solvents.Paper written in the honor of Loren Hepler on the occasion of his retirement.     

The relative permittivity of 1,2-dimethoxyethane and N,N-dimethylformamide mixtures from −10 to 40°C

Binary solutions of N,N-dimethylformamide and 1,2-dimethoxyethane have been investigated by means of dielectric measurements at temperatures ranging from –10 to +40°C, and for nine mixtures covering the whole miscibility field expressed by the mole fraction of one component (0X₁1). The experimental data were used to study the dependence of on T and X₁, of the type = (T), = (X₁), and = (T,X₁). Further, the excess mixing function _E has been evaluated in order to identify particular patterns of interaction between unlike molecules and any other factor that could modify such patterns. The minimum in the _E vs. composition plots suggests the formation of an adduct of stoichiometric ratio DMFDME=11 at all the investigated temperatures.