Catalytic vapor-phase oxidation of p-xylene over tin vanadate

Rates of oxidation of p-xylene were measured in the temperature range 320 to 420 °C using tin vanadate as catalyst in an isothermal differential flow reactor. The amounts of p-xylene converted were determined by analyzing the main products (p-tolualdehyde, maleic anhydride, p-toluic acid and traces of terephthalic acid). Negligible amounts of products of complete combustion were formed. The reaction rates obtained for p-xylene followed the relation, Image based on the redox model. The mechanism of the reaction was determined by conducting different sets of experiments and it was found that the reaction followed the parallel-consecutive mechanism, in which p-tolualdehyde and maleic anhydride were formed from the parallel route whereas p-toluic acid was formed from the consecutive route.

Vapor phase oxidation of p-xylene

The kinetics of the vapor phase oxidation of p-xylene over ferric molybdate catalyst were studied in an isothermal, differential, tubular flow reactor in the temperature range of 360 to 420° C. The major product obtained was p-tolualdehyde with small amounts of maleic anhydride and p-toluic acid. No terephthalic acid or CO2 were observed. The reaction rate data collected fit the redox model given by Equation 1. The values of activation energies Ex, Eo and frequency factors Ax, Ao obtained are 72, 63 kJ/mol and 0.64, 2.89 m3/kg catalyst s respectively. The reaction mechanism was established by studying the oxidation of p-tolualdehyde, toluic and terephthalic acids. It is concluded that the reaction follows a parallel-consecutive scheme. On a étudié la cinétique de l'oxydation, en phase gazeuse, du para-xylène sur un catalyseur consistant en molybdate ferrique; cette oxydation s'est faite dans un réacteur à écoulement tubulaire, isothermique et différentiel, dans une échelle de températures comprises entre 360°C et 420°C. Le produit principal obtenu a été le para-tolualdéhyde; on a aussi trouvé de faibles quantités d'anhydride maléique et d'acide para-toluique, mais on n'a pas noté la présence d'acide téréphtalique ni d'anhydride carbonique (CO2). Les résultats obtenus en ce qui a trait à la vitesse de réaction concordent bien avec les données du modèle redox indiquées par l'équation 1. Les valeurs des énergies d'activation Ex et Eo ainsi que des facteurs de fréquence Ax et Ao obtenus sont respectivement 72 et 63 kilojoules/mol. et 0.64 × 103 et 2.89 m3/kg de catalyseur. On a établi le mécanisme de la réaction en étudiant l'oxydation du para-tolualdéhyde et des acides toluique et téréphtalique. On conclut que la réaction se fait d'une manière parallèle et consécutive.

Vapor-liquid equilibriums: systems methyl ethyl ketone-p-xylene and chlorobenzene-p-xylene

Vapor-liquid equilibrium data have been measured for the binary systems methyl ethyl ketone-p-xylene and chlorobenzene-p-xylene, at 685 mmHg pressure. The activity coefficients have been evaluated taking Into consideration the vapor-phase nonideallty. The f-x-y data have been subjected to a thermodynamic consistency test and the activity coefficients have been correlated by the Wilson equation.

Highly enhanced luminescence from single-crystalline C-60 center dot 1m-xylene nanorods

Single-crystalline C-60 center dot 1m-xylene nanorods with a hexagonal structure were successfully synthesized by evaporating a C-60 solution in m-xylene at room temperature. The ratio of the length to the diameter of the nanorods can be controlled in the range of approximate to 10 to over 1000 for different applications. The photoluminescence (PL) intensity of the nanorods is about 2 orders of magnitude higher than that for pristine C-60 crystals in air. Both UV and Raman results indicate that there is no charge transfer between C-60 and m-xylene. It was found that the interaction between C-60 and m-xylene molecules is of the van der Waals type. This interaction reduces the icosahedral symmetry of C-60 molecule and induces strong PL from the solvate nanorods.

Virtual state scattering with cold electrons: para-xylene and para-difluorobenzene

The scattering of electrons with kinetic energies down to a few meV by para-xylene and para-difluorobenzene has been observed experimentally with an electron beam energy resolution of 0.95 to 1.5 meV (full width half maximum). At low electron energies the collisions can be considered as cold scattering events because the de Broglie wavelength of the electron is considerably larger than the target dimensions. The scattering cross sections measured rise rapidly at low energy due to virtual state scattering. The nature of this scattering process is discussed using s- and p-wave phase shifts derived from the experimental data. Scattering lengths are derived of, respectively, -9.5+/-0.5 and -8.0+/-0.5 a.u. for para-xylene and para-difluorobenzene. The virtual state effect is interpreted in terms of nuclear diabatic and partially adiabatic models, involving the electronic and vibronic symmetries of the unoccupied orbitals in the target species. The concept of direct and indirect virtual state scattering is introduced, through which the present species, in common with carbon dioxide and benzene, scatter through an indirect virtual state process, whereas other species, such as perfluorobenzene, scatter through a direct process. (C) 2005 American Institute of Physics.

Formation of Novel Di-Nuclear Lanthanide Luminescent Sm(III), Eu(III) and Tb(III) Triple Stranded Helicates from a C2 Symmetrically 2,6-Dicarboxylic Amide based 1,3-Xylene Ligand in CH3CN

The synthesis of the C2-symmetrical ligand 1 consisting of two naphthalene units connected to two pyridine-2,6-dicarboxamide moieties linked by a xylene spacer and the formation of LnIII-based (Ln1/4 Sm, Eu, Tb, and Lu) dimetallic helicates [Ln2 · 13] in MeCN by means of a metal-directed synthesis is described. By analyzing the metal-induced changes in the absorption and the fluorescence of 1, the formation of the helicates, and the presence of a second species [Ln2 · 12] was confirmed by nonlinear- regression analysis. While significant changes were observed in the photophysical properties of 1, the most dramatic changes were observed in the metal-centred lanthanide emissions, upon excitation of the naphthalene antennae. From the changes in the lanthanide emission, we were able to demonstrate that these helicates were formed in high yields (ca. 90% after the addition of 0.6 equiv. of LnIII), with high binding constants, which matched well with that determined from the changes in the absorption spectra. The formation of the LuIII helicate, [ Lu2 · 13 ] , was also investigated for comparison purposes, as we were unable to obtain accurate binding constants from the changes in the fluorescence emission upon formation of [Sm2 · 13], [Eu2 · 13], and [Tb2 · 13].

Electron attachment to 2-nitro-m-xylene

Electron attachment to nitroaromatic compound 2-nitro-m-xylene in gas phase has been performed utilizing a double focusing two sector mass spectrometer with high mass resolution (m/Delta m approximate to 2500). At low energy (below 20 eV), electron interactions with the neutral 2-nitro-m-xylene molecule reveal a very rich fragmentation pattern. A total of 60 fragment anions have been detected and the ion yield for all observed negative ions has been recorded as a function of the incident electron energy, among them a long lived (metastable) non-dissociated parent anion which is formed at energies near zero eV, and some ions observed at the mass numbers 26,42 and 121. Comparison of calculated isotopic patterns with measured ion yields for these fragment anions and their successors in the mass spectrum, allows the assignment of the chemical composition of these fragments as CN- (26 Da), CNO- (42 Da) and C8H9O- (121 Da). Electron attachment to 2-nitro-m-xylene leads to anion formation at four energy ranges. Between 0 eV and 2 eV only few product ions are formed. Between 4.6 eV and 6.1 eV all fragment anions are formed and for most of them the anion yield reaches its maximum value in this range. NO2- which is the most abundant product [M-H](-) and O- are the only fragments that exhibit a feature at 7.4eV, 8.1 eV and 7.9eV, respectively. About half of the fragment anions exhibit a broad, mostly low-intensity resonance between 9 eV and 10 eV. (C) 2009 Elsevier B.V. All rights reserved.

Biocomplementation of SVE to achieve clean-up goals in soils contaminated with toluene and xylene

Soil vapor extraction (SVE) and bioremediation (BR) are two of the most common soil remediation technologies. Their application is widespread; however, both present limitations, namely related to the efficiencies of SVE on organic soils and to the remediation times of some BR processes. This work aimed to study the combination of these two technologies in order to verify the achievement of the legal clean-up goals in soil remediation projects involving seven different simulated soils separately contaminated with toluene and xylene. The remediations consisted of the application of SVE followed by biostimulation. The results show that the combination of these two technologies is effective and manages to achieve the clean-up goals imposed by the Spanish Legislation. Under the experimental conditions used in this work, SVE is sufficient for the remediation of soils, contaminated separately with toluene and xylene, with organic matter contents (OMC) below 4 %. In soils with higher OMC, the use of BR, as a complementary technology, and when the concentration of contaminant in the gas phase of the soil reaches values near 1 mg/L, allows the achievement of the clean-up goals. The OMC was a key parameter because it hindered SVE due to adsorption phenomena but enhanced the BR process because it acted as a microorganism and nutrient source.

Acidity and catalytic activity studies on the benzylation of o-xylene using some rare-earth exchanged zeolite-Y

The acidity of the various rare-earth exchanged zeolite-Y catalysts has been examined by titration method using Hammett indicators and is correlated with the catalytic activity of the samples in the benzylation of 0-xylene.

Liquid phase benzylation of o-xylene over pillared clays

Iron, aluminium and mixed iron aluminium pillared clays have been prepared by partial hydrolysis method and doped with IO% Mo, V and Cr. The samples have been characterised by XRD, FTIR and surface area and pore Volume measurements. The surface acid site distribution has been determined by temperature programmed desorption of ammonia. Vanadia incorporated systems show maximum acidity. Benzylation of o-xylene has been done as probe reaction to test catalytic activity. Benzyl chloride is a superior benzylating agent compared to benzyl alcohol in activity and selectivity. Cent percent selectivity towards monobenzylated product is obtained in all the cases. Fe pillared systems exhibit maximum activity. The catalytic activities of the systems can be correlated with the amount of strong add sites. The effects of various reaction variables on the reaction have been studied. Presence of moisture has a diminishing effect on the reaction rate.

Novel nanocomposite fibres for technical textile applications : synthesis and characterisation of poly(m-xylene adipamide) montmorillonite nanocomposites

Technical textiles, based on advanced polymeric materials, are an important segment of the synthetic textile market. This area has seen considerable growth in recent times, now accounting for almost 25% of all manufactured synthetic fibres, and has driven the recent development of a range of specialist high performance polymer fibres that are stronger, lighter or have improved heat and fire resistance. However, the increasing size of the market has highlighted the need for materials that have improved performance whilst maintaining low manufacturing costs. These factors have resulted in a change in how new specialty fibres are developed and the emphasis in this field is now on the upgrading or improving of the properties of commodity (conventional) fibres by modifying their properties to suit specific applications.

This paper will describe our work on preparing novel polymer nanocomposite fibres by the addition of clay nanoparticles during melt extrusion. The effect of the nanoparticles on the processing of the fibres and the result on the physical morphology and mechanical properties will be described.

Nonisothermal Crystallization Behavior of Poly(m-xylene adipamide)/Montmorillonite Nanocomposites

This article reports the nonisothermal crystallization behavior of MXD6 and its clay nanocomposite system (MXD6/MMT) using differential scanning calorimetry (DSC). The DSC experimental data were analyzed by theoretical modeling of the crystallization kinetics using the Avrami, Ozawa, Jeziorny, and the combined Avrami―Ozawa semiempirical models. It has been determined that these models adequately described the crystallization behavior of the MXD6 nanocomposite at cooling rates below 20 °C/min, but there was a deviation from linear dependence at higher cooling rates. This was attributed to changes of both the free energy and the cooling crystallization function K(T) over the entire crystallization process, as well as possible relaxation effects leading to structural rearrangements. In addition, the activation energy determined using the differential isoconversional method of Friedman was also found to vary, indicating changes in both the free energy and crystallization mechanism. Despite the lack of a reliable theoretical model, the heterogeneous nucleating activity of the MMT nanoparticles was demonstrated and quantified using Dobreva's method (Φ = 0.71), and the crystallization rate for the nanocomposite system was found to be greater than pure MXD6 by up to 79% at 40 °C/min.