PREDICTING DIFFUSIVITIES IN DENSE FLUIDS

In this work the Weeks-Chandler-Andersen (WCA) perturbation theory coupled with the Enskog’s solution of the Boltzmann equation for dense hard-sphere fluids is employed for estimating diffusion coefficients in compressed pure liquids and fluids and dense fluid mixtures. The effect of density correction on the estimation of diffusivities is analyzed using the Carnahan-Starling pair correlation function and the correlation of Speedy and Harris which have been proposed as models of self-diffusion coefficient of hard-sphere fluids. The approach presented here is based on the smooth hard-sphere theory without any binary adjustable parameters and can be readily used for estimating diffusivities in multicomponent fluid mixtures. It is shown that the correlated and the predicted diffusivities are in good agreement with the experimental data and much better than estimates of Wilke-Chang equation.

Salting kinetics and salt diffusivities in farmed Pantanal caiman muscle

The legal Pantanal caiman (Caiman crocodilus yacare) farming, in Brazil, has been stimulated and among meat preservation techniques the salting process is a relatively simple and low-cost method. The objective of this work was to study the sodium chloride diffusion kinetics in farmed caiman muscle during salting. Limited volumes of brine were employed, with salting essays carried at 3, 4 and 5 brine/muscle ratios, at 15%, 20% and 25% w/w brine concentrations, and brine temperatures of 10, 15 and 20ºC. The analytical solution of second Fick's law considering one-dimensional diffusion through an infinite slab in contact with a well-stirred solution of limited volume was used to calculate effective salt diffusion coefficients and to predict the sodium chloride content in the fillets. A good agreement was obtained between the considered analytical model and experimental data. Salt diffusivities in fillets were found to be in the range of 0.47x10-10 to 9.62x10-10 m²/s.

A técnica de dispersão de taylor para estudos de difusão em líquidos e suas aplicações

This paper describes the theoretical basis and the experimental requirements for the application of the Taylor dispersion technique for measurements of diffusion coefficients in liquids, emphasizing its simplicity and accuracy in comparison to other usual techniques. Some examples are discussed describing the use of this methodology on studies of solute-solvent interactions, solute aggregation, solute partitioning into macromolecular systems and on the assessment of nanoparticles sizes.

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.

Aplicação da espectroscopia de ressonância magnética nuclear para estudos de difusão molecular em líquidos: a técnica DOSY

Diffusion coefficients provide uniquely detailed and easily interpreted information on molecular organization and phase structure. They are quite sensitive to structural changes, and to binding and association phenomena, in particular for liquid colloidal or macromolecular systems. This paper describes the principles of diffusion measurements in liquids by pulsed magnetic field gradient spin-echo (PFG-SE) NMR spectroscopy. The important PFG-SE technique known as DOSY is presented and discussed. This is a noninvasive technique that can provide individual multicomponent translational diffusion coefficients with good precision in a few minutes, without the need for radioactive isotopic labelling.

O eletrólito suporte e suas múltiplas funções em processos de eletrodo

The aim of this work is to present the principal properties and applications of supporting electrolytes (SE) to students, teachers and researchers interested in electrode processes. Different aspects are discussed including the importance of SE in maintaining constant the activity coefficients and the diffusion coefficients and reducing the transport number of electroactive species. Its effect on the electrochemical kinetic parameters is also presented.

Modelagem e simulação da desidratação osmótica em pedaços de abacaxi utilizando o método de elementos finitos

Water loss and sugar gain were modelling during the osmotic dehydration process of pieces of pineaplle. The transfer of solute to the fruit and the water to the solution was based on Fick's 2nd law. The three dimensional model was solved by the finite element method with the usage of the software COMSOL Multiphysics 3.2. The main and cross diffusion coefficients and the Biot number were determined on the simulation and the deviation between the experimental and the simulated data were 4,28% to sucrose and 1,66 to the water.

Coeficientes de difusão de metais em materiais não convencionais (agarose e acetato de celulose) usados na técnica de difusão em filmes finos por gradientes de concentração

The DGT technique allows one to measure quantitatively free and labile metal species in aquatic systems. Nevertheless, for this approach, knowledge is required of the diffusion coefficients of the analytes in a diffusive layer. In this study, the diffusion coefficients of Hg(II), As(III), Mn(II), Mg(II), Cu(II), Cd(II) were determined in agarose gel and those of Ba(II), Cd(II), Cu(II), Mg(II), Mn(II) e Zn(II) in cellulose acetate membranes. These materials presented good performance and the reported results can be used as a data base for further DGT studies.

COMPREENSÃO MATEMÁTICA DA DIFUSÃO NO CONTEXTO ELETROQUÍMICO

The aim of this study was to explain in detail the mathematical methods used to deal with diffusion equations, mainly for students and researchers interested in electrochemistry and related areas. Emphasis was placed on the deduction and resolution of diffusion equations, as well as addressing cartesian, spherical and cylindrical coordinates. Different aspects of mass transfer processes were discussed including the importance of the resolution of Fick's laws equations to understand and derive parameters of the electroactive species (e.g., diffusion coefficients, formal electrode potentials) from the electrochemical techniques. As an example, the resolution of diffusion equations for a reversible reduction process of soluble oxidized species was presented for the chronopotentiometry technique. This study is envisaged to broaden the understanding of these frequently used methods, in which mathematical deductions are not always completely understood.

Do We Understand Hydrodynamic Dispersion in Sedimenting Suspensions?

Microstructural changes, that is an important feature for the understanding of the velocity variance in sedimentation is investigated with numerical simulations. The simulations are used to describe velocity fluctuations and hydrodynamic dispersion in a suspension of interacting point-particles sedimenting in a rectangular box with periodic sides and impenetrable bottom and top. It is observed how the positions of the particles evolve in a finite container. The suspension that was initially random in the gravity direction only, tends to be fully randomized as a result of the relative arrangements of the particles and the hydrodynamic interactions between them. The computer simulations, based on statistics over a significant number of particle configurations, suggest velocity variances and diffusivities dependent on the size of the simulated system but with anisotropy in velocity fluctuations and diffusion coefficients nearly independent of the box size.

Saline distribution during multicomponent salting in pre-cooked quail eggs

The relationship of NaCl with problems of arterial hypertension has led to a reduction in the levels of this salt in food production. KCl has been used as a partial substitute for NaCl since it cannot be completely substituted without affecting the acceptability of the end product. In this study, the diffusion that occurs during quail egg salting in static and stirred brine was simulated. The mathematical model used was based on a generalization of the Fick's 2nd law, and the COMSOL Multiphysics software was used to simulate the diffusion in the NaCl-KCl-water system. The deviations in the simulated data and experimental data were 2.50% for NaCl and 6.98% for KCl in static brine, while in the stirred brine they were 3.48% for NaCl and 4.72% for KCl. The simulation results presented good agreement with the experimental values and validated the predictive capacity of the model.

Covalidation of Integral Transforms and Method of Lines in Nonlinear Convection-Diffusion with Mathematica

The Mathematica system (version 4.0) is employed in the solution of nonlinear difusion and convection-difusion problems, formulated as transient one-dimensional partial diferential equations with potential dependent equation coefficients. The Generalized Integral Transform Technique (GITT) is first implemented for the hybrid numerical-analytical solution of such classes of problems, through the symbolic integral transformation and elimination of the space variable, followed by the utilization of the built-in Mathematica function NDSolve for handling the resulting transformed ODE system. This approach ofers an error-controlled final numerical solution, through the simultaneous control of local errors in this reliable ODE's solver and of the proposed eigenfunction expansion truncation order. For covalidation purposes, the same built-in function NDSolve is employed in the direct solution of these partial diferential equations, as made possible by the algorithms implemented in Mathematica (versions 3.0 and up), based on application of the method of lines. Various numerical experiments are performed and relative merits of each approach are critically pointed out.

Agronomic performance of 27 cocoa progenies and plant selection based on productivity, self-compatibility and disease resistance

The objective of the present work was to evaluate 27 progenies of cocoa crosses considering the agronomic traits and select F1 plants within superior crosses. The experiment was installed in March 2005, in the Experimental Station Joaquim Bahiana (ESJOB), in Itajuipe, Bahia. The area of the experiment is of approximately 3 ha, with a total of 3240 plants. Thirteen evaluations of vegetative brooms, five of cushion brooms and 15 of number of pods per plant were accomplished. Thirty pollinations were made for each selected plant to test for self-compatibility. The production, based on the number of pods per plant, and resistance to witches´ broom indicated CEPEC 94 x CCN 10, RB 39 x CCN 51 and CCN 10 x VB 1151 as superior progenies. All selections tested were self-compatible. The analyses of progenies and individual tree data, associated to visual field observations, allowed the selection of 17 plants which were included in a network of regional tests to determine the phenotypic stability.

Validity of self-reported weight: a study of urban brazilian adults

In order to evaluate the validity of self-reported weight for use in obesity prevalence surveys, self-reported weight was compared to measured weight for 659 adults living in the Porto Alegre county, RS Brazil in 1986-87, both weights being obtained by a technician in the individual's home on the same visit. The mean difference between self-reported and measured weight was small (-0.06 +/- 3.16 kg; mean +/- standard deviation), and the correlation between reported and measured weight was high (r=0.97). Sixty-two percent of participants reported their weight with an error of < 2 kg, 87% with an error of < 4 kg, and 95% with an error of < 6 kg. Underweight individuals overestimated their weight, while obese individuals underestimated theirs (p<0.05). Men tended to overestimate their weight and women underestimate theirs, this difference between sexes being statistically significant (p=0.04). The overall prevalence of underweight (body mass index < 20) by reported weight was 11%, by measured weight 13%; the overall prevalence of obesity (body mass index > 30) by reported weight was 10%, by measured weight 11%. Thus, the validity of reported weight is acceptable for surveys of the prevalence of ponderosity in similar settings.

The development of a scale to measure concepts of schizophrenia: experience among Brazilian psychiatrists

INTRODUCTION: Among psychiatric disorders schizophrenia is often said to be the condition with the most disputed definition.The Bleulerian and Schneiderian approaches have given rise to diagnostic formulations that have varied with time and place. Controversies over the concept of schizophrenia were examined within European/North American settings in the early 1970s but little has since been reported on the views of psychiatrists in developing countries. In Brazil both concepts are referred to in the literature. A scale was developed to measure adherence to Bleulerian and Schneiderian concepts among psychiatrists working in S. Paulo. METHODOLOGY: A self-reported questionnaire comprising seventeen visual analogue-scale statements related to Bleulerian and Schneiderian definitions of Shizophrenia, plus sociodemographic and training characteristics, was distributed to a non-randomised sample of 150 psychiatrists. The two sub-scales were assessed by psychometric methods for internal consistency, sub-scale structure and test-retest reliability. Items selected according to internal consistency were examined by a two-factor model exploratory factor analysis. Intraclass correlation coefficients described the stability of the scale. RESULTS: Replies were received from 117 psychiatrists (mean age 36 (SD 7.9)), 74% of whom were made and 26% female. The Schneiderian scale showed better overall internal consistency than the Bleulerian scale. Intra-class correlation coefficients for test-retest comparisons were between 0.5 and 0.7 for Schneiderian items and 0.2 and 0.7 for Bleulerian items. There was no negative association between Bleulerian and Schneiderian scale scores, suggesting that respondents may hold both concepts. Place of training was significantly associated with the respondent's opinion; disagreement with a Bleulerian standpoint predominated for those trained at the University of S. Paulo. CONCLUSIONS: The less satisfactory reliability for the Bleulerian sub-scale limits confidence in the whole scale but on the other hand this questionnaire contributes to the understanding of the controversy over Bleulerian and Schneiderian models for conceptualisation of schizophrenia, the former requiring more inference and therefore being prone to unreliability.