Linear relationship between potential and concentration in flow potentiometry

In potentiometric-flow systems, linear-potential responses for logarithmic concentrations can be attained for first-(or pseudo-first-) order reactions in which the monitored chemical species react with the analyte during a fixed time interval. To demonstrate this property, the determination of glycerol based on its oxidation by periodate and potentiometric monitoring of the remaining periodate was selected. Influence of reagent concentration and timing on the linearity of the analytical curve were investigated. A mathematical treatment was derived, and potentialities/limitations of the approach were outlined. The system was applied to analysis of soap and lixivia samples. The analytical curve within 200 and 2000 mg L-1 (r = 0.99975; n = 5) was described as E = 8.166 + 0.0478 (glycerol). The sample throughput was 100 h(-1), and a measurement repeatability within 0.5 mV was always observed. By applying a t-test, there was no statistical difference between the results obtained by the proposed procedure and by iodimetric titration at the 95% confidence level. (C) 2000 John Wiley & Sons, Inc. Lab Robotics and Automation 12:41-45, 2000.

MAGNETOOPTICAL PROPERTIES OF F-2(+) CENTER IN KCL-SH-

The magnetic circular dichroism (MCD) of F2+ centers in KCl:SH- has been measured in absorption in the 1ssigma(g) --> 2p(y)pi(u) transitions at 493 and 509 nm, with fields up to 5 T and in the temperature range 1.5 K < T < 77 K. Within the limit of detection, no MCD is observed in the near infrared transition 1ssigma(g) --> 2psigma(u) as well as in both emissions 2ppi(u) --> 1ssigma(g) and 2psigma(u) --> 1ssigma(g). The optical detection of EPR in the F2+ ground state presents an isotropic single band with g = 1.965 +/- 0.007. The spin-lattice relaxation measured at H = 0.32 T is typical of a direct process T-1 = 4.3 x 10(-2_ coth (gmu(B)H/2k(B)T). The spectral variation of the MCD is calculated using perturbation theory to first order. The Hamiltonian includes the spin-orbit interaction in the 2ppi(u) excited state and the orbital molecular wave functions are obtained by a linear combination of 1s and 2p atomic orbitals. The calculated MCD is in good agreement with the observed one, for the spin-orbit interaction strength Pound(z) = 3.6 meV.

Reduction of mercury(II) by tropical river humic substances (Rio Negro) - A possible process of the mercury cycle in Brazil

The evolution of elemental Hg from its environmental compounds has already been supposed to be an important process within the global mercury cycle. The present study characterizes the abiotic reduction of Hg(II) ions by typical river humic substances (HS) conventionally pre-isolated by the adsorbent XAD 8 from the Rio Negro near Manaus, Brazil. For the investigation of this reduction process a special reaction and Hg(0) trapping unit combined with cold-vapor atomic absorption spectrometry (CVAAS) was developed. Preconcentration of traces of mercury(II), if required, was obtained by a home-made FIA system using microcolumns filled with the Hg(II)-selective collector CheliteS(R) (Serva Company). The effect of environmentally relevant parameters such as the pH value, the Hg(II)/HS ratio and the HS concentration on the I-IE;(II) reduction process was studied as a function of the time. The Hg(0) production was highest at pH 8.0 and in the case of decreasing HS amounts (0.5 mg) when about 65% of initially 1.0 mug Hg(H) was reduced within 50 h. Moreover, the reduction efficiency of HS towards HE;(II) strongly depended on the HS concentration but hardly on the Hg(II)/HS ratio. The reduction kinetics followed a relatively slow two-step first-order mechanism with formal rate constants of about 0.1 and 0.02 h(-1), respectively. Based on these findings the possible relevance of the abiotic evolution of mercury in humic-rich aquatic environments is considered. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Effects of dispersion by Gd3+ upon europium diphenylphosphinate luminescence

A series of binary diphenylphosphinates with Eu3+ and Gd3+ were prepared. The compounds have the general formula Gd1-xEux(DPP)(3), where x ranges from 0 to 1. The spectroscopic measurements show interesting behavior. The intensity of the D-5(0) --> F-7(2) transitions decreases relative to D-5(0) --> F-7(1) With an increase in europium dispersion. Inside the temporal domain, the same decrease is observed with increasing delay after excitation. The lifetimes are also affected, which can be seen in the x = 1 compound, where the decay is a first-order process and lifetime values are 4.81 ms. In the binary compound, as an effect of dispersion, the lifetime of the D-5(0) level measured at the D-5(0) --> F-7(1) transition increases with europium dispersion, and the average along the series is 6.25 ms. The decay measured at the D-5(0) --> F-7(2) transitions reveals a second-order process with lifetimes ranging from 1.90 to 6.00 ms. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Determination of the local site occupancy of Eu3+ ions in ZnAl2O4 nanocrystalline powders

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Bulk and high-energy ball-milled Gd5Si2Ge2: Comparative study of magnetic and magnetocaloric properties

High-energy ball milling was employed to produce small particles of Gd5Si2Ge2. Magnetic and magnetocaloric properties of the ball-milled and bulk Gd5Si2Ge2 samples were investigated through the magnetization measurements. When compared to the bulk material, a significant decrease in saturation magnetization and magnetocaloric effect (-Delta S-max = 4 vs. 20 J/kgK for Delta H = 0-5 T) is observed even after the relatively short ball milling time of 4 h which produced particles with an average size of ca. 0.5 mu m. The ball-milled samples appear to loose a first-order structural transition, present in bulk Gd5Si2Ge2, and display a superparamagnetic behaviour below the corresponding Curie temperatures. (C) 2010 Elsevier Masson SAS. All rights reserved.

Synthesis of a functionalized europium complex and deposition of luminescent Langmuir-Blodgett (LB) films

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

TWO DECOMPOSITION APPROACHES APPLIED TO THE MULTI-AREA OPTIMAL REACTIVE POWER FLOW PROBLEM

This paper applies two methods of mathematical decomposition to carry out an optimal reactive power flow (ORPF) in a coordinated decentralized way in the context of an interconnected multi-area power system. The first method is based on an augmented Lagrangian approach using the auxiliary problem principle (APP). The second method uses a decomposition technique based on the Karush-Kuhn-Tucker (KKT) first-order optimality conditions. The viability of each method to be used in the decomposition of multi-area ORPF is studied and the corresponding mathematical models are presented. The IEEE RTS-96, the IEEE 118-bus test systems and a 9-bus didactic system are used in order to show the operation and effectiveness of the decomposition methods.

Influence of the resonance in a gravity-gradient stabilized satellite

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

Variational studies and replica symmetry breaking in the generalization problem of the binary perceptron

We analyze the average performance of a general class of learning algorithms for the nondeterministic polynomial time complete problem of rule extraction by a binary perceptron. The examples are generated by a rule implemented by a teacher network of similar architecture. A variational approach is used in trying to identify the potential energy that leads to the largest generalization in the thermodynamic limit. We restrict our search to algorithms that always satisfy the binary constraints. A replica symmetric ansatz leads to a learning algorithm which presents a phase transition in violation of an information theoretical bound. Stability analysis shows that this is due to a failure of the replica symmetric ansatz and the first step of replica symmetry breaking (RSB) is studied. The variational method does not determine a unique potential but it allows construction of a class with a unique minimum within each first order valley. Members of this class improve on the performance of Gibbs algorithm but fail to reach the Bayesian limit in the low generalization phase. They even fail to reach the performance of the best binary, an optimal clipping of the barycenter of version space. We find a trade-off between a good low performance and early onset of perfect generalization. Although the RSB may be locally stable we discuss the possibility that it fails to be the correct saddle point globally. ©2000 The American Physical Society.

Analytical/numerical hybrid solution for one-dimensional ablation problem

Ablation is a thermal protection process with several applications in engineering, mainly in the field of airspace industry. The use of conventional materials must be quite restricted, because they would suffer catastrophic flaws due to thermal degradation of their structures. However, the same materials can be quite suitable once being protected by well-known ablative materials. The process that involves the ablative phenomena is complex, could involve the whole or partial loss of material that is sacrificed for absorption of energy. The analysis of the ablative process in a blunt body with revolution geometry will be made on the stagnation point area that can be simplified as a one-dimensional plane plate problem, hi this work the Generalized Integral Transform Technique (GITT) is employed for the solution of the non-linear system of coupled partial differential equations that model the phenomena. The solution of the problem is obtained by transforming the non-linear partial differential equation system to a system of coupled first order ordinary differential equations and then solving it by using well-established numerical routines. The results of interest such as the temperature field, the depth and the rate of removal of the ablative material are presented and compared with those ones available in the open literature.

Modified barrier method for optimal power flow problem

In this paper is presented a new approach for optimal power flow problem. This approach is based on the modified barrier function and the primal-dual logarithmic barrier method. A Lagrangian function is associated with the modified problem. The first-order necessary conditions for optimality are fulfilled by Newton's method, and by updating the barrier terms. The effectiveness of the proposed approach has been examined by solving the Brazilian 53-bus, IEEE118-bus and IEEE162-bus systems.

Ferromagnetic nanoclusters formed by Mn implantation in GaAs

Ferromagnetic clusters were incorporated into GaAs samples by Mn implantation and subsequent annealing. The composition and structural properties of the Mn-based nanoclusters formed at the surface and buried into the GaAs sample were analyzed by x-ray and microscopic techniques. Our measurements indicate the presence of buried MnAs nanoclusters with a structural phase transition around 40 °C, in accord with the first-order magneto-structural phase transition of bulk MnAs. We discuss the structural behavior of these nanoclusters during their formation and phase transition, which is an important point for technological applications. © 2005 American Institute of Physics.

Optimal power flow via interior-exterior method

This paper presents a new approach to the resolution of the Optimal Power Flow problem. In this approach the inequality constraints are treated by the Modified Barrier and Primal-Dual Logarithmic Barrier methods. The inequality constraints are transformed into equalities by introducing positive auxiliary variables, which are perturbed by the barrier parameter. A Lagrangian function is associated with the modified problem. The first-order necessary conditions are applied to the Lagrangian, generating a nonlinear system which is solved by Newton's method. The perturbation of the auxiliary variables results in an expansion of the feasible set of the original problem, allowing the limits of the inequality constraints to be reached. Numerical tests on the Brazilian CESP and South-Southeast systems and a comparative test indicated that the new approach efficiently resolves of the Optimal Power Flow problem. © 2007 IEEE.

A resolução do problema de despacho ótimo de reativos pelo método da função Lagrangiana-barreira relaxada

This work presents the application of the relaxed barrier-Lagrangian function method to the optimal reactive dispatch problem, which is a nonlinear nonconvex and large problem. In this approach the inequality constraints are treated by the association of modified barrier and primal-dual logarithmic barrier method. Those constraints are transformed in equalities through positive auxiliary variables and are perturbed by the barrier parameter. A Lagrangian function is associated to the modified problem. The first-order necessary conditions are applied generating a non-linear system which is solved by Newton's method. The auxiliary variables perturbation result in an expansion of the feasible set of the original problem, allowing the limits of the inequality constraints to be reach. Numeric tests with the systems CESP 53 buses and the south-southeast Brazilian and the comparative test with the primal-dual logarithmic barrier method indicate that presented method is efficient in the resolution of optimal reactive dispatch problem.