Catalytic Hydrogenolysis of Aromatic Ketones in Mixed Choline-Betainium Ionic Liquids

The palladium-catalyzed hydrogenolysis of aromatic ketones to alkylbenzenes was studied in mixtures of ionic liquids to explore the promotional effect of these reaction media. Choline-based ionic liquids displayed complete miscibility with the aromatic ketone substrate at reaction temperature and a clear phase separation of the derived alkylbenzene product at room temperature. Selected ionic liquids were then assessed as reaction media in the hydrogenolysis of aromatic ketones over palladium catalysts. A binary mixture of choline and betainium bis(trifluoromethylsulfonyl)imide ionic liquids resulted in the highest conversion and selectivity values in the hydrogenolysis of acetophenone. At the end of the reaction, the immiscible alkylbenzene separates from the ionic liquid mixture and the pure product phase can be isolated by simple decantation. After optimization of the reaction conditions, high yields (>90%) of alkylbenzene were obtained in all cases. The catalyst and the ionic liquid could be used at least three times without any loss of activity or selectivity.

Visible and Near-Infrared Emission by Samarium(III)-Containing Ionic Liquid Mixtures

Highly luminescent anionic samarium(III) beta-diketonate and dipicolinate complexes were dissolved in the imidazolium ionic liquid 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(6)mim][Tf2N]. The solubility of the complexes in the ionic liquid was ensured by a careful choice of the countercation of the samarium(III) complex. The samarium(III) complexes that were considered are [C(6)mim][SM(tta)(4)], where tta is 2-thenoyltrifluoroacetonate; [C(6)mim][Sm(nta)(4)], where nta is 2-naphthoyltrifluoroacetonate; [C(6)mim][Sm(hfa)(4)], where hfa is hexafluoroacetylacetonate; and [choline](3)-[Sm(dpa)(3)], where dpa is pyridine-2,6-dicarboxylate (dipicolinate) and [choline](+) is (2-hydroxyethyl)trimethyl ammonium. The crystal structures of the tetrakis samarium(III) P-diketonate complexes revealed a distorted square antiprismatic coordination for the samarium(III) ion in all three cases. Luminescence spectra were recorded for the samarium(III) complexes dissolved in the imidazolium ionic liquid as well as in a conventional solvent, that is, acetonitrile or water for the beta-diketonate and dipicolinate complexes, respectively. These experiments demonstrate that [C(6)mim][Tf2N] is a suitable spectroscopic solvent for studying samarium(III) luminescence. High-luminescence quantum yields were observed for the samarium(III) beta-diketonate complexes in solution.

Solvent strength of ionic liquid/CO2 mixtures

Previously we have shown that organic solutes can be extracted from ionic liquids (ILs) with supercritical CO2 and that ILs can be induced to separate from organic and aqueous mixtures by applying gaseous CO2 pressure. Thus, we are interested in the solvent strength of IL/CO2 mixtures. Here we use 4-nitroaniline, N,N-diethyl-4-nitroaniline and Reichardt's dye 33 to determine the Kamlet-Taft parameters for four different imidazolium based ILs and their mixtures with CO2 at 25 and 40degreesC. The effect of temperature and carbon dioxide concentration on these parameters was determined. The polarizability parameter depends weakly on the CO2 concentration. However, the hydrogen bond donating ability and the hydrogen bond accepting ability are virtually independent Of CO2 pressure. The results indicate that the strong interactions between ILs and probe molecules are not influenced by CO2.

Artificial Intelligence Model for Flowable Concrete Mixtures Used in Underwater Construction and Repair

This study explores using artificial neural networks to predict the rheological and mechanical properties of underwater concrete (UWC) mixtures and to evaluate the sensitivity of such properties to variations in mixture ingredients. Artificial neural networks (ANN) mimic the structure and operation of biological neurons and have the unique ability of self-learning, mapping, and functional approximation. Details of the development of the proposed neural network model, its architecture, training, and validation are presented in this study. A database incorporating 175 UWC mixtures from nine different studies was developed to train and test the ANN model. The data are arranged in a patterned format. Each pattern contains an input vector that includes quantity values of the mixture variables influencing the behavior of UWC mixtures (that is, cement, silica fume, fly ash, slag, water, coarse and fine aggregates, and chemical admixtures) and a corresponding output vector that includes the rheological or mechanical property to be modeled. Results show that the ANN model thus developed is not only capable of accurately predicting the slump, slump-flow, washout resistance, and compressive strength of underwater concrete mixtures used in the training process, but it can also effectively predict the aforementioned properties for new mixtures designed within the practical range of the input parameters used in the training process with an absolute error of 4.6, 10.6, 10.6, and 4.4%, respectively.

Effect of Mixture Composition on Relative Strength of Highly Flowable Underwater Concrete

Concrete used for underwater repair is often proportioned to spread readily into place and self-consolidate, and to develop high resistance to segregation and water dilution. An investigation was carried out to determine the effect of the dosage of antiwashout admixture, water-cementitious materials ratio (w/cm), and binder composition on the relative residual strength of highly flowable underwater concrete. Two types of antiwashout admixtures were used: a powdered welan gum at 0.07 and 0.15% by mass of binder, and a liquid-based cellulosic admixture employed at a high dosage of 1 to 1.65 L/100 kg of cementitious materials. The w/cms were set at 0.41 and 0.47 to secure adequate performance of underwater concrete for construction and repair. Four binder compositions were used: a Canadian Type 10 cement; a cement with 10% silica fume replacement; a cement with 50% replacement of granulated blast-furnace slag; and a ternary binder containing 6% silica fume and 20% Class F fly ash. Test results indicate that for a given washout mass loss and slump flow consistency, greater relative residual strength can be secured when the dosage of antiwashout admixture is increased, the w/cm is reduced, and a binary binder with 10% silica fume substitution or the ternary binder are employed. Such mixtures can develop relative residual compressive strengths of 85 and 80%, compared to mixtures cast in air, when the value of washout loss is limited to 4 and 6% for mixtures with slump flow values of 450 and 550 mm, respectively.

Effect of Free-Fall Height in Water on Performance of Flowable Concrete

Concrete placed under water should be proportioned to flow readily into place with minimum materials separation. Unlike concrete cast for deep tremie seals, the use of concrete in repairs often necessitates some free fall of the mixture through water. Such placement conditions lead to greater risk of water erosion and segregation, and should be addressed in proportioning highly flowable underwater concrete. This paper evaluates the effect of free-fall height (FFH) of concrete through water on resulting in-place properties. Concrete was cast in blocks measuring 0.54 x 0.44 x 1 m with the initial FFH in water ranging between 0.25 and 0.60 m. In-place compressive and splitting tensile strengths, unit weight, and depth of washed-out and sedimentation materials were determined. In total, 24 highly flowable mixtures with slump flows greater than 500 mm were investigated. The evaluated mixtures were prepared with various hydraulic binders, including conventional Type 10 cement, a binary mixture with 10% of silica fume (SF), and a ternary binder incorporating 20% of fly ash (FA) and 6% of SF. The mixtures were proportioned with water-binder ratios (w/b) ranging between 0.41 and 0.47. Test results show that the increase of FFH of fresh concrete in water can greatly decrease the residual strength and significantly increase the thickness of washed out and sedimentation materials. The incorporation of 10% of SF, or 20% of FA and 6% of SF, and the reduction of the w/b from 0.47 to 0.41 can, however, lead to a significant increase in washout resistance and residual strength. A relationship between residual strength and the coupled factor of free-fall drop of concrete in water and washout resistance is established.

Reactivity of ammonium chloride/mercuric chloride mixtures with monel containers. The new compounds (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] and (NH4)(5)Cl-2[CuCl2][CuCl4]

Ammonium chloride/mercuric chloride mixtures (molar ratio 2: 1) react at 350degreesC with Monel (Cu68Ni32) to yield (NH4)NiCl3 and mercury and copper amalgam, respectively. With larger amounts of (NH4)Cl in the reaction mixture, dark green (NH4)(2)(NH3)(x)[Ni(NH3)(2)Cl-4] (x approximate to 0.77) (1) is also formed as a main product. Light blue crystals of the mixed-valent copper(I,II) chloride (NH4)(5)Cl-5[CuCl2][CuCl4] (2) were obtained as a minor byproduct from a 4:1 reaction mixture. The crystal structures were determined from single crystal X-ray data; (1): tetragonal, I4/mmm, a = 770.9(1), e = 794.2(2) pm, 190 reflections, R-1 = 0.0263; (2): tetragonal, I4/mcm, a = 874.8(1), c = 2329.2(3) pm, 451 reflections, R-1 = 0.0736. In (1) Ni2+ resides in trans-[Ni(NH3)(2)Cl-4](2-) octahedra, and in (2) copper(l) is linearly two-coordinated in ECUC121- and copper(II) resides in a flattened tetrahedron [CuCl4](2-) with a tetrahedricity of 89%. (C) 2001 Elsevier Science.

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO2. It was found that a highly hydroxylated surface of blank SnO2 reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO2 the sensor signal maximum towards H-2 in dry air (R-0/R-g) is observed at similar to 345 degrees C, and towards water, at similar to 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO2 is unchanged. The interaction of hydrogen with the catalyst doped SnO2 occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H-2 by a factor of 1000.

Separation of acid-dyes mixture by bamboo derived active carbon

In the present study, the activated carbon is produced using phosphoric acid treatment of the waste bamboo scaffolding and activated at either 400 or 600 °C. The effect of acid to bamboo ratio (Xp) up to 2.4 has been studied. The BET surface area increased with increasing Xp and activating temperature. BET surface area up to 2500 m2/g carbon has been produced. In order to simulate effluent treatment from textile industry, the produced carbon was tested for its dye adsorption capacities. Two acid dyes with different molecular sizes were used, namely Acid Yellow 117 (AY117) and Acid Blue 25 (AB25). In a single component system, it was found that dye with smaller molecular size, AB25, was readily adsorbed onto the carbon while the larger size dye, AY117, showed little adsorption. As a result, it is possible to tailor-make the carbon for the adsorption of dye mixtures in industrial applications, especially textile dyeing, i.e. molecular sieve effect. A binary AY117–AB25 mixture was used to test the possibility of the molecular sieve effect. Furthermore, experimental results were fitted to equilibrium isotherm models, Langmuir, Freundlich and Sips for the single component system. For the binary component system, extended single-component equilibrium isotherm models were used to predict the experimental data.

MML 53: a new low-mass, pre-main sequence eclipsing binary in the Upper Centaurus-Lupus region discovered by SuperWASP

We announce the discovery of a new low-mass, pre-main sequence eclipsing binary, MML 53. Previous observations of MML 53 found it to be a pre-main sequence spectroscopic multiple associated with the 15-22 Myr Upper Centaurus-Lupus cluster. We identify the object as an eclipsing binary for the first time through the analysis of multiple seasons of time series photometry from the SuperWASP transiting planet survey. Re-analysis of a single archive spectrum shows MML 53 to be a spatially unresolved triple system of young stars which all exhibit significant lithium absorption. Two of the components comprise an eclipsing binary with period, P = 2.097891(6) ± 0.000005 and mass ratio, q ~ 0.8. Here, we present the analysis of the discovery data.

Abell 41: shaping of a planetary nebula by a binary central star

ABSTRACT We present the first detailed spatiokinematical analysis and modelling of the planetary nebula Abell 41, which is known to contain the well-studied close-binary system MT Ser. This object represents an important test case in the study of the evolution of planetary nebulae with binary central stars as current evolutionary theories predict that the binary plane should be aligned perpendicular to the symmetry axis of the nebula. Deep narrow-band imaging in the light of [NII]6584Å, [OIII]5007 Å and [SII]6717+6731Å, obtained using ACAM on the William Herschel Telescope, has been used to investigate the ionization structure of Abell 41. Long-slit observations of the Ha and [NII]6584Å emission were obtained using the Manchester Echelle Spectrometer on the 2.1-m San Pedro Mártir Telescope. These spectra, combined with the narrow-band imagery, were used to develop a spatiokinematical model of [NII]6584Å emission from Abell 41. The best-fitting model reveals Abell 41 to have a waisted, bipolar structure with an expansion velocity of ~40 km s-1 at the waist. The symmetry axis of the model nebula is within 5° of perpendicular to the orbital plane of the central binary system. This provides strong evidence that the close-binary system, MT Ser, has directly affected the shaping of its nebula, Abell 41. Although the theoretical link between bipolar planetary nebulae and binary central stars is long established, this nebula is only the second to have this link, between nebular symmetry axis and binary plane, proved observationally.