Considerações sobre a eletrogeração de peróxido de hidrogênio

This paper presents some results that may be used as previous considerations to a hydrogen peroxide electrogeneration process design. A kinetic study of oxygen dissolution in aqueous solution is carried out and rate constants for oxygen dissolution are calculated. Voltammetric experiments on vitreous carbon cathode shown that the low saturation concentration drives the oxygen reduction process to a mass transfer controlled process which exhibits low values of limiting currents. Results have shown that the hydrogen peroxide formation and its decomposition to water are separated by 400 mV on the vitreous carbon surface. Diffusion coefficients for oxygen and hydrogen peroxide are calculated using data taken from Levich and Tafel plots. In a series of bulk electrolysis experiments hydrogen peroxide was electrogenerated at several potential values, and concentration profiles as a function of the electrical charged passed were obtained. Data shown that, since limiting current plateaus are poorly defined onto reticulated vitreous carbon, cathodic efficiency may be a good criterion for choosing the potential value in which hydrogen peroxide electrogeneration should be carried out.

Revisió del model inclusiu en l’àmbit de l’educació no formal del futbol base a partir del criteri d’agrupació

Recerca centrada en l’anàlisi de característiques concretes de l’educació inclusiva en un entorn d’educació no formal, com és el futbol base. El criteri que s’ha utilitzat per realitzar l’anàlisi són els agrupaments. Des de l’educació inclusiva es promouen els agrupaments heterogenis, una forma d’agrupar a l’alumnat tenint en compte les seves diferències, per tal d’enriquir-se entre tot l’alumnat i treure profit d’elles. A la vegada aquest agrupament es caracteritza per fomentar la igualtat d’oportunitats en l’aprenentatge dels alumnes. En canvi, al futbol base predominen els agrupaments homogenis, distribuint als jugadors segons el seu nivell en diferents equips. A la recerca es fa una comparació entre l’opinió de diferents membres involucrats en el món del futbol base de dues entitats esportives, un club de futbol, on es fan els grups de forma homogènia, i una escola de futbol, on es fan els agrupaments de forma heterogènia. Els resultats mostren que realitzant agrupaments homogenis no s’assegura que tots els jugadors tinguin les mateixes oportunitats d’aprenentatge i que el nivell competencial dels jugadors en edat de formació pot ser un element que fomenti desigualtats en el seu procés d’aprenentatge esportiu.

Construindo o estágio de docência da pós-graduação em química

The teaching apprenticeship established by CAPES for post-graduation scholarship beholders has been discussed and the criterion adopted for the implementation in the post-graduation in Inorganic Chemistry Program presented. A teaching plan for the new subject is proposed, based on the experience gained through a first group. An instrument for evaluation of the student's performance has been developed and analyzed. Aspects like knowledge, clearness, enthusiasm, confidence, good manage on the audio-visual resources, class length are mentioned by degree of importance and the major difficulties faced and pointed out by the students.

Scale-up model obtained from the rheological analysis of highly concentrated emulsions prepared at three scales

We examine the scale invariants in the preparation of highly concentrated w/o emulsions at different scales and in varying conditions. The emulsions are characterized using rheological parameters, owing to their highly elastic behavior. We first construct and validate empirical models to describe the rheological properties. These models yield a reasonable prediction of experimental data. We then build an empirical scale-up model, to predict the preparation and composition conditions that have to be kept constant at each scale to prepare the same emulsion. For this purpose, three preparation scales with geometric similarity are used. The parameter N¿D^α, as a function of the stirring rate N, the scale (D, impeller diameter) and the exponent α (calculated empirically from the regression of all the experiments in the three scales), is defined as the scale invariant that needs to be optimized, once the dispersed phase of the emulsion, the surfactant concentration, and the dispersed phase addition time are set. As far as we know, no other study has obtained a scale invariant factor N¿Dα for the preparation of highly concentrated emulsions prepared at three different scales, which covers all three scales, different addition times and surfactant concentrations. The power law exponent obtained seems to indicate that the scale-up criterion for this system is the power input per unit volume (P/V).

Estabilidade relativa de alcenos: análise dos critérios encontrados nos livros textos de graduação e uma proposta de explicação operacional para alcenos dissubstituídos

Despite of being used as thermodynamic criterion to rank alkene stability in a number of undergraduate textbooks, the heat of hydrogenation does not describe adequately the relative stability of disubstituted alkenes. In this work, both the heat of formation and the heat of combustion were used as thermodynamic criteria to rank correctly the stability of alkenes according to the degree of alkyl substitution and also in the disubstituted series (geminal > trans > cis). An operational model based on molecular orbital and valence bond representations of hyperconjugation is proposed to show how this effect can explain the order of stability of this class of compounds.

Predictors of smoking craving during virtual reality exposure

Cue exposure treatment (CET) consists of controlled and repeated exposure to drugrelated stimuli in order to reduce cue-reactivity. Virtual reality (VR) has proved to be a promising tool for exposition. However, identifying the variables that can modulate the efficacy of this technique is essential for selecting the most appropriate exposure modality. The aim of this study was to determine the relation between several individual variables and self-reported craving in smokers exposed to VR environments. Fortysix smokers were exposed to seven complex virtual environments that reproduce typical situations in which people smoke. Self-reported craving was selected as the criterion variable and three types of variables were selected as the predictor variables: related to nicotine dependence, related to anxiety and impulsivity, and related to the sense of presence in the virtual environments. Sense of presence was the only predictor of self-reported craving in all the experimental virtual environments. Nicotine dependence variables added predictive power to the model only in the virtual breakfast at home. No relation was found between anxiety or impulsivity and self-reported craving. Virtual reality technology can be very helpful for improving CET for substance use disorders. However, the use of virtual environments would make sense only insofar as the sense of presence was high. Otherwise, the effectiveness of exposure might be affected. © 2012 by the Massachusetts Institute of Technology.

A characterization of cooperative TU-games with large monotonic core

[cat] El concepte de joc cooperatiu amb large core és introduït per Sharkey (1982) i el de Population Monotonic Allocation Scheme és definit per Sprumont (1990). Inspirat en aquests conceptes, Moulin (1990) introdueix la noció de large monotonic core donant una caracterització per a jocs de tres jugadors. En aquest document provem que tots els jocs amb large monotonic core són convexes. A més, donem un criteri efectiu per determinar si un joc té large monotonic core o no, i daquí obtenim una caracterització pel cas de quatre jugadors.

A characterization of cooperative TU-games with large monotonic core

[cat] El concepte de joc cooperatiu amb large core és introduït per Sharkey (1982) i el de Population Monotonic Allocation Scheme és definit per Sprumont (1990). Inspirat en aquests conceptes, Moulin (1990) introdueix la noció de large monotonic core donant una caracterització per a jocs de tres jugadors. En aquest document provem que tots els jocs amb large monotonic core són convexes. A més, donem un criteri efectiu per determinar si un joc té large monotonic core o no, i daquí obtenim una caracterització pel cas de quatre jugadors.

Setting priorities in clinical and health services research: Properties of an adapted and updated method

Objectives: The objectives of this study is to review the set of criteria of the Institute of Medicine (IOM) for priority-setting in research with addition of new criteria if necessary, and to develop and evaluate the reliability and validity of the final priority score. Methods: Based on the evaluation of 199 research topics, forty-five experts identified additional criteria for priority-setting, rated their relevance, and ranked and weighted them in a three-round modified Delphi technique. A final priority score was developed and evaluated. Internal consistency, test–retest and inter-rater reliability were assessed. Correlation with experts’ overall qualitative topic ratings were assessed as an approximation to validity. Results: All seven original IOM criteria were considered relevant and two new criteria were added (“potential for translation into practice”, and “need for knowledge”). Final ranks and relative weights differed from those of the original IOM criteria: “research impact on health outcomes” was considered the most important criterion (4.23), as opposed to “burden of disease” (3.92). Cronbach’s alpha (0.75) and test–retest stability (interclass correlation coefficient = 0.66) for the final set of criteria were acceptable. The area under the receiver operating characteristic curve for overall assessment of priority was 0.66. Conclusions: A reliable instrument for prioritizing topics in clinical and health services research has been developed. Further evaluation of its validity and impact on selecting research topics is required

A Practical Micro Mechanical Model Based Local Approach Methodology for the Analysis of Ductile Fracture of Welded T-Joints

This thesis concentrates on developing a practical local approach methodology based on micro mechanical models for the analysis of ductile fracture of welded joints. Two major problems involved in the local approach, namely the dilational constitutive relation reflecting the softening behaviour of material, and the failure criterion associated with the constitutive equation, have been studied in detail. Firstly, considerable efforts were made on the numerical integration and computer implementation for the non trivial dilational Gurson Tvergaard model. Considering the weaknesses of the widely used Euler forward integration algorithms, a family of generalized mid point algorithms is proposed for the Gurson Tvergaard model. Correspondingly, based on the decomposition of stresses into hydrostatic and deviatoric parts, an explicit seven parameter expression for the consistent tangent moduli of the algorithms is presented. This explicit formula avoids any matrix inversion during numerical iteration and thus greatly facilitates the computer implementation of the algorithms and increase the efficiency of the code. The accuracy of the proposed algorithms and other conventional algorithms has been assessed in a systematic manner in order to highlight the best algorithm for this study. The accurate and efficient performance of present finite element implementation of the proposed algorithms has been demonstrated by various numerical examples. It has been found that the true mid point algorithm (a = 0.5) is the most accurate one when the deviatoric strain increment is radial to the yield surface and it is very important to use the consistent tangent moduli in the Newton iteration procedure. Secondly, an assessment of the consistency of current local failure criteria for ductile fracture, the critical void growth criterion, the constant critical void volume fraction criterion and Thomason's plastic limit load failure criterion, has been made. Significant differences in the predictions of ductility by the three criteria were found. By assuming the void grows spherically and using the void volume fraction from the Gurson Tvergaard model to calculate the current void matrix geometry, Thomason's failure criterion has been modified and a new failure criterion for the Gurson Tvergaard model is presented. Comparison with Koplik and Needleman's finite element results shows that the new failure criterion is fairly accurate indeed. A novel feature of the new failure criterion is that a mechanism for void coalescence is incorporated into the constitutive model. Hence the material failure is a natural result of the development of macroscopic plastic flow and the microscopic internal necking mechanism. By the new failure criterion, the critical void volume fraction is not a material constant and the initial void volume fraction and/or void nucleation parameters essentially control the material failure. This feature is very desirable and makes the numerical calibration of void nucleation parameters(s) possible and physically sound. Thirdly, a local approach methodology based on the above two major contributions has been built up in ABAQUS via the user material subroutine UMAT and applied to welded T joints. By using the void nucleation parameters calibrated from simple smooth and notched specimens, it was found that the fracture behaviour of the welded T joints can be well predicted using present methodology. This application has shown how the damage parameters of both base material and heat affected zone (HAZ) material can be obtained in a step by step manner and how useful and capable the local approach methodology is in the analysis of fracture behaviour and crack development as well as structural integrity assessment of practical problems where non homogeneous materials are involved. Finally, a procedure for the possible engineering application of the present methodology is suggested and discussed.

The role of aromaticity in determining the molecular structure and reactivity of (endohedral metallo)fullerenes

The encapsulation of metal clusters in endohedral metallofullerenes (EMFs) takes place in cages that in most cases are far from being the most stable isomer in the corresponding hollow fullerenes. There exist several possible explanations for the choice of the hosting cages in EMFs, although the final reasons are actually not totally well understood. Moreover, the reactivity and regioselectivity of (endohedral metallo)fullerenes have in the past decade been shown to be generally dependent on a number of factors, such as the size of the fullerene cage, the type of cluster that is being encapsulated, and the number of electrons that are transferred formally from the cluster to the fullerene cage. Different rationalizations of the observed trends had been proposed, based on bond lengths, pyramidalization angles, shape and energies of (un)occupied orbitals, deformation energies of the cages, or separation distances between the pentagon rings. Recently, in our group we proposed that the quest for the maximum aromaticity (maximum aromaticity criterion) determines the most suitable hosting carbon cage for a given metallic cluster (i.e. EMF stabilization), including those cases where the IPR rule is not fulfilled. Moreover, we suggested that local aromaticity plays a determining role in the reactivity of EMFs, which can be used as a criterion for understanding and predicting the regioselectivity of different reactions such as Diels-Alder cycloadditions or Bingel-Hirsch reactions. This review highlights different aspects of the aromaticity of fullerenes and EMFs, starting from how this can be measured and ending by how it can be used to rationalize and predict their molecular structure and reactivity

Typen oksidien mittausepävarmuuden määrittäminen ilmanlaatumittauksille

Euroopan unionin direktiiveissä ja kansallisessa lainsäädännössä on asetettu tavoitteita, velvoitteita ja raja-arvoja ilmanlaadun mittauksille. Ilmanlaatua on seurattava, ilmanlaatumittaukset on tehtävä laadukkaasti sekä luotettavasti ja mittaustuloksista on tiedotettava väestölle. Mittausten epävarmuus on tunnettava ja sen on oltava alle 15 %, jotta epävarmuudelle asetettu kriteeri täyttyy. Tässä työssä perehdyttiin Euroopan unionin ilmastopolitiikkaan ja kansalliseen ilmanlaatua koskevaan lainsäädäntöön, käytiin läpi menetelmiä ja tapoja, joilla ilmanlaadusta tiedotetaan väestölle sekä selvitettiin ilmanlaadun mittausjärjestelmiä koskevia vaatimuksia. Ennen varsinaista mittausepävarmuuden selvittämistä käytiin läpi tutkimuksen kohteena olevan typen oksidien analysaattorin mittausperiaate ja merkittävimmät komponentit. Mittausepävarmuus määritettiin standardia SFS-EN 14211 noudattamalla. Mittausepävarmuuden selvittämiseksi analysaattorille tehtiin erilaisia sen toimintaa kuvaavia testejä Ilmatieteen laitoksen kalibrointilaboratoriossa. Saatujen tuloksien perusteella voitiin laskea analysaattorin mittausepävarmuus, joka tuntiraja-arvopitoisuudessa oli 15,5 % ja vuosiraja-arvopitoisuudessa 10,5 %. Kaikkia testejä ei voitu tehdä standardissa määrätyllä tavalla, joten tuloksiin pitää suhtautua kriittisesti. Tulosten perusteella mittausepävarmuus tuntiraja-arvopitoisuudessa ei aivan täytä direktiivin kriteeriä, mutta vuosiraja-arvopitoisuudessa kriteeri täyttyy (< 15 %).

An Interface Damage Model for the Simulation of Delamination Under Variable-Mode Ratio in Composite Materials

A thermodynamically consistent damage model for the simulation of progressive delamination under variable mode ratio is presented. The model is formulated in the context of the Damage Mechanics. The constitutive equation that results from the definition of the free energy as a function of a damage variable is used to model the initiation and propagation of delamination. A new delamination initiation criterion is developed to assure that the formulation can account for changes in the loading mode in a thermodynamically consistent way. The formulation proposed accounts for crack closure effets avoiding interfacial penetration of two adjacent layers aftercomplete decohesion. The model is implemented in a finite element formulation. The numerical predictions given by the model are compared with experimental results

Sobre a primeira lei da termodinâmica: as diferenciais do calor e do trabalho

We treat some subtleties concerning the First Law of Thermodynamics and discuss the inherent difficulties, namely the interpretation of the heat and the work differentials. By proposing a new differential equation for the First Law, which is written using both system and neighborhood variables, we overcome the mentioned difficulties and establish a criterion for the definition of heat and work.

Empirical welfare analysis: when preferences matter

Fleurbaey and Maniquet have proposed the criteria of conditional equality and of egalitarian equivalence to assess the equity among individuals in an ordinal setting. Empirical applications are rare and only partially consistent with their framework. We propose a new empirical approach that relies on individual preferences, is consistent with the ordinal criteria and enables to compare them with the cardinal criteria. We estimate a utility function that incorporates individual heterogeneous preferences, obtain ordinal measures of well-being and apply conditional equality and egalitarian equivalence. We then propose two cardinal measures of well-being, that are comparable with the ordinal model, to compute Roemer’s and Van de gaer’s criteria. Finally we compare the characteristics of the worst-off displayed by each criterion. We apply this model to a sample of US micro data and obtain that about 18% of the worst-off are not common to all criteria.