Antimony Solubility and Speciation in Aqueous Sulphuric Acid Solutions at 298 K

This work is an experimental and theoretical study of antimony speciation and the solubility of Sb₂O₅, Sb₂O₃ and Sb₂(SO₄)₃ at 298 K in aqueous sulphuric acid solutions (0 to 6 kmol/m³). A thermodynamic model was developed to quantify the solubility products and aqueous metal speciation. Main dissolved species were H₃SbO_3(aq) and H₃SbO_4(aq). The solubility of antimony increases with increasing solution acidity and with the presence of hydrogen peroxide in the solution. The following standard equilibrium constants at 298 K were obtained: Log K⁰_(Sb2O5) = 11.7±0.5, Log K⁰_(Sb2O3) = 32±1, and Log K⁰_(Sb2(SO4)3) = 55±2.     

Thermal stability of NO 2 ⋅ and NO⋅ radicals formed in an Al23 catalyst during its preparation from a nitrate precursor

During the preparation of alumina as a catalyst support from aluminium nitrates by precipitation with a NH₄OH base, NO ₂ ^⋅ radicals have been formed in the catalyst after calcination under air in the solid at different temperatures. These radicals remained stable until a calcination temperature of 800°C. When the calcined catalyst was degassed under vacuum above 300 °C, the NO ₂ ^⋅ was reduced to give NO^⋅ and O^- species which were both tightly trapped in the solid. These latter species remained stable until vacuum treatment at 800 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Barocalorimetric technique for monitoring pressurized copolymer reactors

The problem of on‐line estimation of the conversion and composition evolutions in a pressurized batch copolymer reactor with temperature and pressure measurements was addressed. The estimation model consisted of mass and energy balances with a pressure equation built from phase‐equilibrium considerations. The application of a nonlinear geometric estimation approach yielded the underlying solvability condition with physical meaning, a straightforward estimator construction, and a conventional‐like tuning procedure. The resulting barocalorimetric estimator was an on‐line dynamic measurement processor with a model‐based predictor and a measurement‐driven corrector, and whose implementation did not require the polymerization rates and heat‐transfer coefficient function dependencies. The technique was tested with a representative laboratory styrene–butadiene system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 475–482, 2005     

Studies of the activation process over Pd perovskite-type oxides used for catalytic oxidation of toluene

Calcined and reduced catalysts Pd/LaBO₃ (B = Co, Fe, Mn, Ni) were used for the total oxidation of toluene. Easiness of toluene destruction was found to follow the sequence based on the T₅₀ values (temperature at which 50% of toluene is converted): Pd/LaFeO₃ > Pd/LaMnO_3+δ > Pd/LaCoO₃ > Pd/LaNiO₃. In order to investigate the activation process (calcination and reduction) in detail, the reducibility of the samples was evaluated by H₂-TPR on the calcined catalysts. Additionally, characterization of the Pd/LaBO₃ (B = Co, Fe) surface was carried out by X-ray photoelectron spectroscopy (XPS) at each stage of the global process, namely after calcination, reduction and under catalytic reaction at either 150 or 200 °C for Pd/LaFeO₃ and either 200 or 250 °C for LaCoO₃. The different results showed that palladium oxidized entities were totally reduced after pre-reduction at 200 °C for 2 h (2 L/h, 1 °C/min). As LaFeO₃ was unaffected by such a treatment, for the other perovskites, the cations B are partially reduced as B³⁺ (B = Mn) or B²⁺ even to B⁰ (B = Co, Ni). In the reactive stream (0.1% toluene in air), Pd⁰ reoxidized partially, more rapidly over Co than Fe based catalysts, to give a Pd²⁺/Pd⁴⁺ and Pd⁰/Pd²⁺/Pd⁴⁺ surface redox states, respectively. Noticeably, reduced cobalt species are progressively oxidized on stream into Co³⁺ in a distorted environment. By contrast, only the lines characteristic of the initial perovskite lattice were detected by XRD studies on the used catalysts. The higher activity performance of Pd/LaFeO₃ for the total oxidation of toluene was attributed here to a low temperature of calcination and to a remarkable high stability of the perovskite lattice whatever the nature of the stream which allowed to keep a same palladium dispersion at the different stages of the process and to resist to the oxidizing experimental conditions. On the contrary, phase transformations for the other perovskite lattices along the process were believed to increase the palladium particle size responsible of a lower activity.     

Modelling the dynamics of the students’ academic performance in the German region of the North Rhine-Westphalia: an epidemiological approach with uncertainty

Student academic underachievement is a concern of paramount importance in Europe, where around 15% of the students in the last high school courses do not achieve the minimum knowledge academic requirement. In this paper, we propose a model based on a system of differential equations to study the dynamics of the students’ academic performance in the German region of the North Rhine-Westphalia. This approach is supported by the idea that both good and bad study habits, are a mixture of personal decisions and influence of classmates. This model allows us to forecast the student academic performance by means of confidence intervals over the next few years.     

Synthesis and characterization of epoxidized styrene–butadiene rubber/silicon dioxide hybrid materials

Hybrid materials were synthesized from epoxidized (68, 43, or 14%) styrene–butadiene rubber (SBR) and the hydrolysis product of tetraethoxysilane (TEOS) in situ under ultrasonic irradiation. The products were characterized with thermal analysis (differential scanning calorimetry and thermogravimetric analysis), stress–strain tests, scanning electron microscopy (including energy‐dispersive spectrometry), and swelling in tetrahydrofuran and water. The most transparent were those prepared from SBR with the highest degree of epoxidation, whereas those obtained from less epoxidized SBR and with larger amounts of TEOS showed distinct phases that could be considered two hybrid phases (one rich in TEOS and another rich in SBR). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 798–803, 2004     

Simple and economic syntheses of some (Z)-7- and (Z)-9-alkenyl acetates,and of (E,Z)-7,9-dodecadien-1-yl acetate,the sex pheromone of the European grapevine moth,using aleuritic acid as a common starting material

Short syntheses of (Z)-7-dodecen-1-yl acetate, (Z)-7-tetradecen-1-yl acetate, (Z)-9-dodecen-1-yl acetate, and (Z)-9-tetradecen-1-yl acetate from 7-hydroxyheptanal and 9-oxononanoic acid precursors obtained by oxidative cleavage of easily available aleuritic acid are reported. The key step in these syntheses is a stereoselective Wittig reaction between aldehyde and alkyl-phosphonium salt. Wittig-Horner type reaction of 7-hydroxyheptanal and diethyl cyanomethylphosphonate gave the ,-unsaturated nitrile derivative which after protection of the hydroxyl group was reduced to the corresponding aldehyde. Wittig reaction of the latter, followed by acetylation, completed the synthesis of (E,Z)-7,9-dodecadien-1-yl acetate, the sex pheromone of the European grapevine mothLobesia botrana Schiff.     

CALIBRATION OF THE METHOD TO MEASURE BUBBLE PROPERTIES IN 2D FLUIDIZED BEDS

The purpose of the present work is to demonstrate the reliability of a digital image processing technique. A CCD (Charge Coupled Device) is used to perform an investigation on the bubble properties of a 2D gas-solid fluidized bed, and the aim of this study is to establish a criterion in order to reject all images that could not be interpreted as bubbles. This may lead to an alteration of the information obtained. The two-dimensional fluidized bed is 20 cm wide and at least 20 cm high, and the field of view of the camera is 12.54 cm wide and 12.99 cm high. In this way, bubbles could be totally or partially placed into this field of view so that a partial image of a bubble could be analyzed as a whole bubble. With this calibration, a geometric decision criterion for the rejection of nonbubble images was developed.     

Catalyst’s Sulfur Displacement by Thiophene, as Monitored by Exchange of 35S Radiotracer

The isotopic exchange has been studied between catalyst radiosulfur and H₂S, formed in thiophene hydrodesulfurization (HDS) (named S-displace) on alumina supported molybdena, on CoMoO_x, PdMoO_x, PtMoO_x and on silica–alumina supported NiWO_x. S-displace was compared with radiosulfur exchange data between catalyst radiosulfur and gas phase H₂S (S^exc) determined previously. The extent of S^exc was higher than that of the S-displace for Mo, CoMo in and NiW, whereas the extent of S-displace from PdMoO and PtMoO was significantly higher, than that of S^exc. Thiophene HDS product distribution data are discussed in terms of increased C=C hydrogenation and C–C hydrogenolysis activity, explained by increasing H₂S production with longer circulation time of the thiophene/H₂ mixture, The C₁/C₃<1 ratios among C₄-hydrogenolysis products indicate some coke formation. The decrease of thiophene HDS activity is presumably a consequence of increasing site-blocking with the formation of more H₂S and coke with longer duration of thiophene treatment.     

Reciprocal Tree-Like Fractal Structures

Sometimes the complex structures of nature inspire human constructions. Gothic construction has shown that forces can cross space along intricate paths that may even be arbitrary if correctly dimensioned. In some way, ribbed structures are like trees where the branches conduct forces instead of sap; they operate as branches and trunks descending by fractal ways. Here we discuss reciprocal tree-like fractal structures and the difficulty in their design and erection and solutions for constructive details, as well as the possible analytical questions and automatic generation by means of proper software. The results are shown in the design of the Natural Interpretation Centre in Melilla where we have proposed two connected trees like shown at figures included below.