Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.

Solid mass falling into the reservoirs shallow water equations validity from the engineering point of view

Water waves generated by a solid mass is a complex phenomenon discussed in this paper by numerical and experimental approaches. A model based on shallow water equations with shocks (Saint Venant) has developed. It can reproduce the amplitude and the energy of the wave quite well, but because it consistently generates a hydraulic jump, it is able to reproduce the profile, in the case of high relative thickness of slide, but in the case of small relative thickness it is unable to reproduce the amplitude of the wave. As the momentum conservation is not verified during the phase of wave creation, a second technique based on discharge transfer coefficient α, is introduced at the zone of impact. Numerical tests have been performed and validated this technique from the experimental results of the wave's height obtained in a flume.

Sintering and mass transport features of (Sn,Ti)O2 polycrystalline ceramics

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.

Time reduction in a forced-convection thermal process using simplified transient analysis

This study investigates the utilisation of a simplified model in the transient analysis of a thermal cooling process. In such process the external thermal resistance between the surface and the surroundings is high compared to the system internal thermal resistance, so that the first controls the heat transfer process. In this case the Biot number is lower than 0.1. Aluminium reels were utilised, which, with proper internal instrumentation, furnished experimental results for the thermal cooling process. Based on experimental data, a simplified model for the determination of the process film coefficient was used. Subsequently, experimental and theoretical results were compared. The change of the airflow direction was also investigated for the cooling process, aiming at process time optimisation. (C) 2001 Elsevier B.V. Ltd.

An investigation on parallel, divergent and convergent acetylene dual jet diffusion flames

Results are presented and discussed of an experimental investigation on acetylene turbulent dual jet diffusion flames. The study includes parameters of flames in parallel, divergent and convergent configurations. Tests with two parallel jets with addition of helium in the fuel stream were also performed and analysed. The variation of overall flame length and of other name physical characteristics, such as width, volume and conditions for lifting, are presented as functions of burner tip Reynolds number, jet distance from each other and inclination angle. The effects of diluent concentration in the fuel gas stream are presented for single and two parallel jets. (C) 1999 Elsevier B.V. Ltd.

Effective diffusion coefficients behavior in osmotic dehydration of apple slices considering shrinking and local concentration dependence

The mass transfer during osmotic dehydration of apple slices immersed in 40, 50 and 60% (w/w) aqueous sucrose solutions was investigated to evaluate the influence of solution concentration on diffusivities. In the mathematical model, the diffusion coefficients were functions of the local water and sucrose concentration. The mass transfer equations were, simultaneously, solved for water and sucrose using an implicit numerical method. Material coordinates following the shrinkage of the solid were used. The predicted concentration profiles were integrated and compared to experimental data, showing a reasonable agreement with the measured data. on average, the effective diffusion coefficients for water and sucrose decreased as the osmotic solution concentration increased; that is the behavior of the binary coefficients in water-sucrose solutions. However, the diffusivities expressed as a function of the local concentration in the slices varied between the treatments. Water diffusion coefficients showed a remarkable variation throughout the slice and unusual behavior, which was associated to the cellular structure changes observed in tissue immersed in osmotic solutions. Cell structure changes occurred in different ways: moderate plasmolysis at 40%, accentuated plasmolysis at 50% and generalized damage of the cells at 60%. Intact vacuoles were observed after a long time of exposure (30 h) to 40 and 50% solutions. Effects of the concentration on tissue changes make it difficult to generalize the behavior of diffusion coefficients.

Influência de pré-influência de pré-tratamentos sobre a desidratação osmótica de carambolas

A desidratação osmótica (DO) de fatias de carambola (Averrhoa carambola L.) em solução de sacarose foi estudada, com o objetivo de otimizar o processo. Num primeiro conjunto de experimentos, aplicou-se revestimento de coberturas comestíveis (pectina ou pectina+amido) sobre as fatias, seguido de do em solução aquosa de sacarose (50%, p/p, 27°C). Num segundo conjunto, foi realizada secagem parcial da cobertura, em estufa, antes da DO. Num terceiro conjunto de experimentos testou-se a adição de CaCl2 na solução osmótica. A aplicação dos revestimentos antes da do não melhorou a eficiência (máxima perda água/ganho soluto) devido à grande retenção de umidade e à fácil impregnação de sacarose nos mesmos, enquanto que o tecido vegetal sem revestimento restringiu mais o ganho de soluto e propiciou maior saída de água. A utilização de CaCl2 a 0,04M, na própria solução osmótica de sacarose, melhorou ligeiramente a eficiência do processo, em relação à solução sem o sal. A do em solução de sacarose, sem e com a adição de CaCl2, geraram resultados positivos na qualidade sensorial da carambola em fatias, desidratadas em secador (60 e 70°C), em comparação com a fruta não tratada, sendo que a melhor temperatura de secagem foi 60°C.

Kinetics of osmotic dehydration and air-drying of pumpkins (Cucurbita moschata)

Kinetics of osmotic dehydration (OD) and effects of sucrose impregnation on thermal air-drying of pumpkin slices were investigated. A simplified model based on the solution of Fick's Law was used to estimate effective diffusion coefficients during OD and air-drying. In order to take into account shrinkage, average and variable thicknesses were considered. Pumpkin slices were dehydrated in sucrose solutions (40%, 50% and 60%, w/w, 27 degrees C. The effective water diffusion coefficients were higher than the sucrose, and low diffusivity dependence with solution concentration was observed. Samples non-treated and pre-treated in 60% osmotic solutions during one hour were dried in a hot-air-dryer at 50 and 70 degrees C (2 m/s) until equilibrium was achieved. Pre-treatment enhanced mass transfer during air-drying. Great volume reduction was observed in pre and non-treated dried samples. Using variable thickness in the model diminished the relative deviations between predicted and experimental OD and drying data. (C) 2007 Elsevier Ltd. All rights reserved.

A new approach for thermal performance calculation of cross-flow heat exchangers

A new numerical methodology for thermal performance calculation in cross-flow heat exchangers is developed. Effectiveness-number of transfer units (epsilon-NTU) data for several standard and complex flow arrangements are obtained using this methodology. The results are validated through comparison with analytical solutions for one-pass cross-flow heat exchangers with one to four rows and with approximate series solution for an unmixed-unmixed heat exchanger, obtaining in all cases very small errors. New effectiveness data for some complex configurations are provided. (c) 2005 Elsevier Ltd. All rights reserved.

Cinética de dissolução da superfície de aço SAE-AISI 1005 em meio ácido

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

Salting kinetics and salt diffusivities in farmed Pantanal caiman muscle

A criação de jacaré do Pantanal (Caiman crocodilus yacare) em cativeiro tem sido estimulada, e entre as técnicas de processamento de sua carne, a salga é um processo de conservação relativamente simples e de baixo custo. O objetivo deste trabalho foi estudar a cinética de difusão de cloreto de sódio em carne de jacaré do Pantanal criado em cativeiro, durante a salga úmida. Foram utilizados volumes limitados de salmoura e os experimentos foram realizados com relações salmoura/músculo de 3, 4 e 5, com concentrações de salmoura de 15%, 20% e 25% em peso e temperaturas de 10, 15 e 20ºC. A solução analítica da segunda lei de Fick, considerando difusão unidimensional em uma placa infinita em contato com uma solução bem agitada de volume limitado, foi utilizada para calcular os coeficientes de difusão efetivos de sal e estimar o conteúdo de cloreto de sódio nos filés. Obteve-se boa concordância entre o modelo analítico considerado e os dados experimentais. As difusividades do sal nos filés ocorreram na faixa de 0,47x10-10 a 9,62x10-10 m²/s.

Estimativa da composição gasosa em embalagem de atmosfera modificada contendo mangas (mangifera indica l.) Cv. Keitt

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The Chemical Percolation Devolatilization Model Applied to the Devolatilization of Coal in High Intensity Acoustic Fields

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Supercritical fluid extraction from fennel (Foeniculum vulgare): global yield, composition and kinetic data

Supercritical fluid extraction (SFE) from solids has proven to be technically feasible for almost any system; nonetheless, its economical viability has been proven for a restricted number of systems. A common practice is to compare the cost of manufacturing of vegetable extracts by a variety of techniques without deeply considering the huge differences in composition and functional properties among the various types of extracts obtained; under this circumstance, the cost of manufacturing do not favor SFE. Additionally, the influence of external parameters such as the agronomic conditions and the SFE system geometry are not considered. In the present work, these factors were studied for the system fennel seeds + CO2. The effects of the harvesting season and the degree of maturation on the global yields for the system fennel seeds + CO2 were analyzed at 300 bar and 40 degrees C. The effects of the pressure on the global yields were determined for the temperatures of 30 and 40 degrees C. Kinetics experiments were done for various ratios of bed height to bed diameter. Fennel extracts were also obtained by hydrodistillation and low-pressure solvent extraction. The chemical composition of the fennel extracts were determined by gas chromatography. The SFE maximum global yield (12.5%, dry basis) was obtained with dry harvested fennel seeds. Anethole and fenchone were the major constituents of the extract; the following fat acids palmitic (C16H32O2), palmitoleic stearic (C18H36O2), oleic (C18H34O2), linoleic (C18H32O2) and linolenic (C18H30O2) were also detected in the extracts. A relation between amounts of feed and solvent, bed height and diameter, and solvent flow rate was proposed. The models of Sovova, Goto et al. and Tan and Lion were capable of describing the mass transfer kinetics. (c) 2005 Elsevier B.V. All rights reserved.

Effective thermal conductivity of beans via a steady-state method

Steady-state concentric cylinder equipment was used to determine the effective thermal conductivity of beans (Phaseolus vulgaris). The measuring cell had no heated end guards and its length to diameter ratio was 10.5. Glass beads were employed to assess the accuracy and repeatability of the experimental system under heat transfer conditions. The results agree well with those reported in the literature so that the system can be considered reliable. Corn was used to verify the system's accuracy under heat and mass transfer conditions. Again the results were satisfactory. Moisture migration was observed and measured during the tests with beans, but this behavior does not compromise thermal conductivity values if both thermal and mass transfer steady-states are correctly interpreted. The effective thermal conductivity increases linearly with increasing grain moisture content. Statistical regression leads to good estimates of the fitted parameters.