958 resultados para STANDARD GIBBS ENERGIES OF TRANSFER
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In this Special Issue, the focus is on contact-induced language variation and change in situations of societal bilingualism that involve long-term contact between French and another language. As is well known, when two or more languages are spoken by groups of speakers in the same geographical area, over time, features from one language can be transferred to the other language, especially when the languages in question are unequal in terms of prestige, institutional support and demographic factors. The process that leads to the adoption of such features in the contact languages is generally known as INTERFERENCE or TRANSFER, and these terms are also used to describe the features in question (i.e. the end product of the process of transfer). In this issue we prefer to use the term TRANSFER over the use of the notion INTERFERENCE, as the former has fewer negative connotations than the latter.
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In the present study, the mycosporine-like amino acids (MAAs) were isolated from the marine red alga Gracilaria tenuistipitata and analysed by high-resolution accurate-mass sequential mass spectrometry (MSn). In addition to the proposed fragmentation mechanism based on the MSn analysis, it is clearly demonstrated that the elimination of mass 15 is a radical processes taking place at the methoxyl substituent of the double bond. This characteristic loss of a methyl radical was studied by theoretical calculations and the homolytic cleavage of the O-C bond is suggested to be dependent on the bond weakening. The protonation site of the MAAs was indicated by analysis of the Fukui functions and the relative Gibbs energies of the several possible protonated forms. (C) 2008 Elsevier B.V. All rights reserved.
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The electrooxidation of small organic molecules on platinum surfaces usually involves different structure-dependent steps that include adsorption and desorption of various species and multiple reaction pathways. Because temperature plays a decisive role on each individual step, understanding its global influence on the reaction mechanism is often a difficult task, especially when the system is studied under far from equilibrium conditions in the presence of kinetic instabilities. Aiming at contributing to unravel this problem, herein, we report an experimental study of the role played by temperature on the electrooxidation of formic acid on a Pt(100) electrode. The system was investigated under both close and far from equilibrium conditions, and apparent activation energies were estimated using different strategies. Overall, comparable activation energies were estimated under oscillatory and quasi-stationary conditions, at high potentials. At low potentials, the poisoning process associated with the formic acid dehydration step presented a negligible dependence with temperature and, therefore, zero activation energy. On the basis of our experimental findings, we suggest that formic acid dehydration is the main, but maybe not the unique, step that differentiates the temperature dependence of the oscillatory electrooxidation of formic acid on Pt(100) with that on polycrystalline platinum.
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This study examined how the standard metabolic rate of tegu lizards, a species that undergoes large ontogenetic changes in body weight with associated changes in life-history traits, is affected by changes in body mass, body temperature, season, and life-history traits. We measured rates of oxygen consumption ((V) over dot o(2)) in 90 individuals ranging in body mass from 10.4. g to 3.75 kg at three experimental temperatures ( 17 degrees, 25 degrees, and 30 degrees C) over the four seasons. We found that standard metabolic rate scaled to the power of 0.84 of body mass at all experimental temperatures in all seasons and that thermal sensitivity of metabolism was relatively low (Q(10) approximate to 2.0-2.5) over the range from 17 degrees to 30 degrees C regardless of body size or season. Metabolic rates did vary seasonally, being higher in spring and summer than in autumn and winter at the same temperatures, and this was true regardless of animal size. Finally, in this study, the changes in life-history traits that occurred ontogenetically were not accompanied by significant changes in metabolic rate.
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The ground state masses and binding energies of the nucleon, lambda0, lambdac+ , lambdab0 are studied within a constituent quark QCD-inspired light-front model. The light-front Faddeev equations for the Qqq composite spin 1/2 baryons, are derived and solved numerically. The experimental data for the masses are qualitatively described by a flavor independent effective interaction.
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Using the hyperspherical adiabatic approach in a coupled-channel calculation, we present precise binding energies of excitons trapped by impurity donors in semiconductors within the effective-mass approximation. Energies for such three-body systems are presented as a function of the relative electron-hole mass sigma in the range 1 less than or equal to1/sigma less than or equal to6, where the Born-Oppenheimer approach is not efficiently applicable. The hyperspherical approach leads to precise energies using the intuitive picture of potential curves and nonadiabatic couplings in an ab initio procedure. We also present an estimation for a critical value of sigma (sigma (crit)) for which no bound state can be found. Comparisons are given with results of prior work by other authors.
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Within the approach of supersymmetric quantum mechanics associated with the variational method a recipe to construct the superpotential of three-dimensional confined potentials in general is proposed. To illustrate the construction, the energies of the harmonic oscillator and the Hulthen potential, both confined in three dimensions are evaluated. Comparison with the corresponding results of other approximative and exact numerical results is presented. (C) 2003 Elsevier B.V. All rights reserved.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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The accuracy of impressions that transfer the relationship of the implant to the metal framework of the prosthesis continues to be a problem. This study was designed to evaluate the accuracy of the transfer process under variable conditions with regard to implant analog angulations, impression materials, and techniques. Replicas (n = 60) of a metal matrix (control) containing four implants at 90°, 80°, 75°, and 65° in relation to the horizontal surface were obtained by using three impression techniques: T1 - indirect technique with conical copings in closed trays; T2 - direct technique with square copings in open trays; and T3 - square copings splinted with autopolymerizing acrylic resin; and four elastomers: P-polysulfide; I-polyether; A-addition silicone; and Z-condensation silicone. The values of the implant analog annulations were assessed by a profilometer to the nearest 0.017°, then submitted to analysis of variance for comparisons at significance of 5% (P < .05). For implant analog at 90°, the material A associated with T2 and material Z with T3 behaved differently (P < .05) from all groups. At 80°, all materials behaved differently (P < .01) with T1. At 75°, when T1 was associated, materials P and A showed similar behavior, as well as materials I and Z; however, P and A were different from I and Z (P < .01). When T3 was associated, all experimental groups behaved differently among them (P < .01). At 65°, the materials P and Z behaved differently (P < .01) from the control group with T1, T2, and T3; the materials I and A behaved differently from the control group (P < .01) when T1 and T2, respectively, were associated. The more perpendicular the implant analog annulation is in relation to the horizontal surface, the more accurate the impression. The best materials were material I and A and the most satisfactory technique was technique 3.
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Purpose: This study evaluated the influence of surface abrasion of transfer copings to obtain a precise master cast for a partially edentulous restoration with different inclinations. Materials and Methods: Replicas (N = 30) of a metal matrix (control group) containing two implants at 90° and 65° in relation to the benchtop were obtained using a polyether impression material and three impression techniques: square impression copings splint with dental floss and autopolymerizing acrylic resin (TRS), square impression copings abraded with aluminum oxide (TA), and square impression copings abraded with aluminum oxide and adhesive-coated (TAA). The replicas obtained in type V stone were digitalized, and the images were exported to AutoCAD software to perform the readings of possible degree alterations in implant inclinations. The results were submitted to analysis of variance (ANOVA) and Tukey test (α < 0.05). Results: Comparing the techniques with regard to the 90° implant inclination, no statistical difference was observed between the three techniques and the control group. Analyzing the three techniques with regard to the 65° implant inclination, no significant difference was seen between technique TA and the control group. Conclusions: Technique TA presented more accurate master casts than TRS and TAA techniques. The angulated implant (65°) tended to generate more imprecise master casts than implants perpendicular to the surface. © 2008 by The American College of Prosthodontists.
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Water-miscible ionic liquids (ILs) may be salted out using kosmotropic salts such as potassium phosphate (K3PO4) to form salt-salt aqueous biphasic systems (ABS). The effect of temperature on these systems has been studied using phase diagrams and it is observed that the degree of binodal shift decreases (requiring lower IL and kosmotropic salt concentrations) with the increase of temperature following the trend [C(4)mim]Cl > [C(4)py]Cl > [C(4)mmim] Cl > [N-4444]Cl. This trend can be correlated with the decreasing hydrogen bonding abilities of each salt. The phase behavior was also interpreted on the basis of critical solution temperature behavior of pure aqueous ionic liquid solutions. Additionally, the distribution of alcohols in these systems was studied as a function of temperature and it was found that the distribution ratios did not change with changes in temperature. The Gibbs energy of transfer of a methylene group in these systems and correlation to tie-line length was also determined. It was concluded that while the miscibility of alcohols increases in the ILs with increasing temperature, phase divergence in the aqueous biphasic system decreases, and thus these competing forces tend to cancel each other out for small polar molecules. A comparison is provided for the response to temperature in the currently studied salt-salt systems and analogous ABS formed by the addition of hydrophilic polymers to kosmotropic salts (polymer-salt) or other polymers (polymer-polymer).
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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The present study deals with the determination of the activation energy for the thermal decomposition of two renewable fuels crude glycerin and beef tallow. The activation energies were investigated by using a thermogravimetric analyzer (TGA) in the temperature range of 25-600 degrees C in atmosphere of synthetic air. The TG curves of the thermal decomposition process of both samples were divided into several phases and the second, called PH2, was chosen for the kinetic study because it is associated with the combustion ignition. Differential Thermal Analysis (DTA) showed an endothermic event at the PH2 region for the crude glycerin corresponding to devolatilization, while for beef tallow, this step presented an exothermic event, called LTO (low-temperature oxidation), which is correlated with devolatilization followed by combustion. For the entire PH2, activation energy values for crude glycerin were between 90 kJ mol(-1) and 42 kJ mol(-1), while for the beef tallow they ranged from 50 kJ mol(-1) to 113 kJ mol (1). The activation energy values obtained at the pre-ignition stage - conversion between 0 and 0.45 - showed that the crude glycerin with higher values requires an additional energetic support at the start of combustion processes and the beef tallow ignites more easily, presenting lower values. According to the Wolfer's equation, a direct relation between the activation energy and the ignition delay is established and the results of this study provides useful data for the development and design of new combustion chambers and engines when non-traditional fuels are used as feedstock. (C) 2012 Elsevier Ltd. All rights reserved.