59 resultados para intrinsic equilibrium constants


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Ant communities are sensitive to fragmentation responding through: extinction of specialist species compared with large habitats, invasion of generalist species, changes in community composition and richness of species. Because of these characteristics, this review aims at examining the main risks that ants have been facing to maintain their communities, as well as to report current conservation practices in Brazil and in the world.

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The kinetics of the hexacyanoferrate(III)-N,N′-dimethyl-4,4′-bipyridinium radical (MV+) reaction was studied by a laser flash photolysis technique. The radical was generated, in the presence of Fe(CN)6 3-, by quenching the excited state *Ru(bpy)3 2+ with MV2+. The second-order rate constant for the Fe(CN)6 3--MV+ reaction is (7.6 ± 0.5) × 109 M-1 s-1 at 23°C and ionic strength 0.10 M. Comparison with the rate constants calculated for the diffusion-controlled reaction (4.7 × 109 M-1 s-1) and the activation-controlled reaction (5.2 × 1012 M-1 s-1, on the basis of self-exchange rate constants of 8.0 × 105 M-1 s-1 and 1.9 × 104 M-1 s-1 for the MV2+/+ and Fe(CN)6 3-/4- couples, respectively) leads to the conclusion that the Fe(CN)6 3--MV+ reaction is diffusion controlled. The rate constant for the Fe(CN)6-MV2+ reaction, calculated from the rate constant for the Fe(CN)6 3--MV+ reaction and the appropriate equilibrium constant, is 2.4 × 10-5 M-1 s-1 at 23°C and ionic strength 0.10 M. Microscopic reversibility considerations require that the Fe(CN)6 4--MV2+ reaction be controlled by the dissociation of the successor complex Fe(CN)6 3-|MV+. The thermal and optical electron transfers in the ion pair Fe(CN)6 4-|MV2+ and in related systems are analyzed and discussed. © 1982 American Chemical Society.

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The equilibrium and kinetics of methemoglobin conversion to hemichrome induced by dehydration were investigated by visible absorption spectroscopy. Below about 0.20 g water per g hemoglobin only hemichrome was present in the sample; above this value, an increasing proportion of methemoglobin appeared with the increase in hydration. The transition between the two derivatives showed a time-dependent biphasic behavior and was observed to be reversible. The rates obtained for the transition of methemoglobin to hemichrome were 0.31 and 1.93 min-1 and for hemichrome to methemoglobin 0.05 and 0.47 min-1. We suggest that hemichrome is a reversible conformational state of hemoglobin and that the two rates observed for the transition between the two derivatives reflect the α- and β-chains of hemoglobin.

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Mathematical programming problems with equilibrium constraints (MPEC) are nonlinear programming problems where the constraints have a form that is analogous to first-order optimality conditions of constrained optimization. We prove that, under reasonable sufficient conditions, stationary points of the sum of squares of the constraints are feasible points of the MPEC. In usual formulations of MPEC all the feasible points are nonregular in the sense that they do not satisfy the Mangasarian-Fromovitz constraint qualification of nonlinear programming. Therefore, all the feasible points satisfy the classical Fritz-John necessary optimality conditions. In principle, this can cause serious difficulties for nonlinear programming algorithms applied to MPEC. However, we show that most feasible points do not satisfy a recently introduced stronger optimality condition for nonlinear programming. This is the reason why, in general, nonlinear programming algorithms are successful when applied to MPEC.

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Different (Sn,Ti)O2 compositions were sintered at 1450 °C for 2 h with the purpose of investigating their sintering and mass transport properties. Highly dense ceramics were obtained and their structural properties studied by X-ray diffraction and scanning electron microscopy. The changes in lattice parameters were analyzed by the Rietveld method and two mass transport mechanisms were observed during sintering in different temperature ranges, evidenced by the linear shrinkage rate as a function of temperature. The effect of the concentration of TiO2 on mass transport and densiffication during sintering was analyzed by considering the intrinsic defects. System densiffication was attributed to a mass transport mechanism in the SnO2 matrix, caused by the presence of TiO2, which formed a solid solution phase. The change in the mass transport mechanism was attributed to chemical bonding between SnO2 and TiO2, which improves ionic difusion as the concentration of TiO2 increased in (Sn,Ti)O2 compositions. © 2002 Elsevier Science Ltd. All rights reserved.

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A correction procedure based on digital signal processing theory is proposed to smooth the numeric oscillations in electromagnetic transient simulation results from transmission line modeling based on an equivalent representation by lumped parameters. The proposed improvement to this well-known line representation is carried out with an Finite Impulse Response (FIR) digital filter used to exclude the high-frequency components associated with the spurious numeric oscillations. To prove the efficacy of this correction method, a well-established frequency-dependent line representation using state equations is modeled with an FIR filter included in the model. The results obtained from the state-space model with and without the FIR filtering are compared with the results simulated by a line model based on distributed parameters and inverse transforms. Finally, the line model integrated with the FIR filtering is also tested and validated based on simulations that include nonlinear and time-variable elements. © 2012 Elsevier Ltd. All rights reserved.

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In this paper, we consider a concept of local Nash equilibrium for non-cooperative games - the so-called weak local Nash equilibrium. We prove its existence for a significantly more general class of sets of strategies than compact convex sets. The theorems on existence of the weak local equilibrium presented here are applications of Brouwer and Lefschetz fixed point theorems. © 2013 Juliusz Schauder Centre for Nonlinear Studies Nicolaus Copernicus University.

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We report the structural and magnetic properties of Co2MnO 4, partially substituted by Bi at the octahedral site. Bismuth enhances ferromagnetism due to a decrease of the Co2+-Co2+ antiferromagnetic interactions and an increase of the Mn3+-Mn 4+ exchanges. Spurious phases (magnetic and/or nonmagnetic oxides) can easily form because of the large differences between the ionic radii of Bi3+ and Co3+, hiding or altering the intrinsic physical properties of the main BixCo2-xMnO4 phase. An easy way to eliminate the secondary phases is using acid reagents. Short-time etching of Bi0.1Co1.9MnO4 using nitric acid was successfully used, keeping most of the properties of the initial compound, with no alteration of the crystallographic structure. Final stoichiometry was respected (∼Bi0.08Co1.82MnO4), meaning that the material after etching definitely contains bismuth elements in its structure and the observed properties are intrinsic to the oxide spinel. Additional experiments were performed as a function of the synthesis conditions, showing that an optimal pH value of 7 allowed the best magnetic response of the non-doped material. © 2013 Elsevier B.V. All rights reserved.

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Aquaporins have important roles in various physiological processes in plants, including growth, development and adaptation to stress. In this study, a gene encoding a root-specific tonoplast intrinsic aquaporin (TIP) from Eucalyptus grandis (named EgTIP2) was investigated. The root-specific expression of EgTIP2 was validated over a panel of five eucalyptus organ/tissues. In eucalyptus roots, EgTIP2 expression was significantly induced by osmotic stress imposed by PEG treatment. Histochemical analysis of transgenic tobacco lines (Nicotiana tabacum SR1) harboring an EgTIP2 promoter:GUS reporter cassette revealed major GUS staining in the vasculature and in root tips. Consistent with its osmotic-stress inducible expression in eucalyptus, EgTIP2 promoter activity was up-regulated by mannitol treatment, but was down-regulated by abscisic acid. Taken together, these results suggest that EgTIP2 might be involved in eucalyptus response to drought. Additional searches in the eucalyptus genome revealed the presence of four additional putative TIP coding genes, which could be individually assigned to the classical TIP1-5 groups. © 2013 Elsevier B.V.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The pH values near a planar dissociating membrane are studied under a mean field approximation using the Poisson-Boltzmann equation and its linear form. The equations are solved in planar symmetry with the consideration that the charge density on the dissociating membrane surface results from an equilibrium process with the neighboring electrolyte. Results for the membrane dissociation degree are presented as a function of the electrolyte ionic strength and membrane surface charge density. Our calculations indicate that pH values have an appreciable variation within 2 nm from the membrane. It is shown that the dissociation process is enhanced due to the presence of bivalent ions and that pH values acquire better stability than in an electrolyte containing univalent ions.

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The objective of this work is to develop a non-stoichiometric equilibrium model to study parameter effects in the gasification process of a feedstock in downdraft gasifiers. The non-stoichiometric equilibrium model is also known as the Gibbs free energy minimization method. Four models were developed and tested. First a pure non-stoichiometric equilibrium model called M1 was developed; then the methane content was constrained by correlating experimental data and generating the model M2. A kinetic constraint that determines the apparent gasification rate was considered for model M3 and finally the two aforementioned constraints were implemented together in model M4. Models M2 and M4 showed to be the more accurate among the four developed models with mean RMS (root mean square error) values of 1.25 each.Also the gasification of Brazilian Pinus elliottii in a downdraft gasifier with air as gasification agent was studied. The input parameters considered were: (a) equivalence ratio (0.28-035); (b) moisture content (5-20%); (c) gasification time (30-120 min) and carbon conversion efficiency (80-100%). (C) 2014 Elsevier Ltd. All rights reserved.