986 resultados para apparent activation energy


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The electrical conductivity of a range of concrete mixes, with and without supplementary cementitious materials (SCM), is studied through multiple cycles of heating and cooling over the extended temperature range −30/+70 °C. When presented in an Arrhenius format, the experimental results display hysteresis effects at the low-temperature end of the thermal cycle and, in those concretes containing supplementary cementitious materials at higher water/binder ratios, hysteresis effects were evident over the entire temperature range becoming more discernible with increasing number of thermal cycles. The depression in both the freezing and thawing point could be clearly identified and was used to estimate pore-neck and pore-cavity radii. A simplified approach is presented to evaluate the volumetric ratio of frozen pore water in terms of conductivity measurements. The results also show that the conductivity and activation energy of the concrete specimens were related to the water/binder ratio, type of SCM, physical state of the pore water and the thermal cycling regime.

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The batch-operated bromate/phosphate/acetone/dual catalyst system was studied at four temperatures between 5 and 35 degrees C. The dynamics was simultaneously followed by potential measurements with platinum and bromide selective electrodes, and spectroscopically at two different wavelengths. By simultaneously recording these four time series it was possible to characterize the dynamics of the sequential oscillations that evolve in time. The existence of three sequential oscillatory patterns at each temperature allowed estimating the activation energies in each case. Along with the activation energy of the induction period, it was possible to trace the time evolution of the overall activation energy at four different stages as the reaction proceeds. The study was carried out for two different sets of initial concentrations and it was observed that the overall activation energy increases as reactants turn into products. This finding was propounded as a result of the decrease in the driving force, or the system`s affinity, of the catalytic oxidative bromination of acetone with acidic bromate, as the closed system evolves toward the thermodynamic equilibrium.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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The eutectoid transformation may be defined as a solid-state diffusion-controlled decomposition process of a high-temperature phase into a two-phase lamellar aggregate behind a migrating boundary on cooling below the eutectoid temperature. In substitutional solid solutions, the eutectoid reaction involves diffusion of the solute atoms either through the matrix or along the boundaries or ledges. The effect of Ag on the non-isothermal kinetics of the reverse eutectoid reaction in the Cu-9 mass%Al, Cu-10 mass%Al, and Cu-11 mass%Al alloys were studied using differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The activation energy for this reaction was obtained using the Kissinger and Ozawa methods. The results indicated that Ag additions to Cu-Al alloys interfere on the reverse eutectoid reaction, increasing the activation energy values for the Cu-9 mass%Al and Cu-10 mass%Al alloys and decreasing these values for the Cu-11 mass%Al alloy for additions up to 6 mass%Ag. The changes in the activation energy were attributed to changes in the reaction solute and in Ag solubility due to the increase in Al content.

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The digestible energy and apparent nutrient digestibility coefficients of common diet ingredients were determined for pacu Piaractus brachypomus (370.21 ± 17.56 g). Fish were fed with pelleted practical diets to apparent satiation and the feces were collected by siphoning. The digestibility value for each ingredient was determined by comparison of the digestibility of a test diet with a reference diet (24.5% crude protein and 1% chromic oxide). The digestible energy values of soybean meal (SBM), fish meal (FM), corn (CN), and wheat bran (WB) were 2382, 3826, 3353, and 1784 kcal/kg, respectively. The apparent dry matter digestibility coefficients were 83.72, 90.14, 89.13, and 82.05% for SBM, FM, CN, and WB, respectively. The apparent crude protein digestibility coefficients were 75.88, 90.49, 85.06, and 61.62% for SBM, FM, CN, and WB, respectively. The apparent lipid digestibility coefficients were 63.03, 77.00, 83.01, and 82.45% for SBM, FM, CN, and WB, respectively. The digestibility of protein, lipid, and energy from SBM were somewhat low compared to values for other warmwater omnivorous fishes, but similar to values reported for pacu-caranha P. mesopotamicus. Otherwise, the nutrient and energy availability of the ingredients to P. brachypomus was similar to that of other fish. This information will be useful in formulating nutritious, economical diets for pacus. © by the World Aquaculture Society 2004.

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With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99%) under visible light irradiation at ambient temperature. Au/zeolite photocatalysts were characterized by UV/Vis, XPS, TEM, XRD, EDS, BET, IR, and Raman techniques. The Surface Plasmon Resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports, and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range, and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterization data and the photocatalytic performances, we proposed a possible photooxidation mechanism.

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TiO2 nanofibers with different crystal phases have been discovered to be efficient catalysts for the transesterification of alcohols with dimethyl carbonate to produce corresponding methyl carbonates. Advantages of this catalytic system include excellent selectivity (>99%), general suitability to alcohols, reusability and ease of preparation and separation of fibrous catalysts. Activities of TiO2 catalysts were found to correlate with their crystal phases which results in different absorption abilities and activation energies on the catalyst surfaces. The kinetic isotope effect (KIE) investigation identified the rate-determining step, and the isotope labeling of oxygen-18 of benzyl alcohol clearly demonstrated the reaction pathway. Finally, the transesterification mechanism of alcohols with dimethyl carbonate catalyzed by TiO2 nanofibers was proposed, in which the alcohol released the proton to form benzyl alcoholic anion, and subsequently the anion attacks the carbonyl carbon of dimethyl carbonate to produce the target product of benzyl methyl carbonate.

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The changes in the tensile properties and fracture mode brought about by heat treatment of Fe-12Cr-6Al ferritic stainless steel have been studied. A favourable combination of high strength and good ductility is obtained by heating the material at 1370 K for 2 h followed by a water quench. The high-temperature treatment results in carbide dissolution as well as an increase in the grain size. The mechanism of strengthening has been evaluated from the apparent activation energy (28 kJ mol–1) and is identified to be the unpinning of dislocations from the atmosphere of carbon atoms. As the heat-treatment temperature is increased, the fracture behaviour changes from ductile to brittle mode and this is related to the changes in grain size and friction stress.