Electro-oxidation of ethanol on Pt/C, Rh/C, and Pt/Rh/C-based electrocatalysts investigated by on-line DEMS

The ethanol electro-oxidation reaction was studied on carbon-supported Pt, Rh, and on Pt overlayers deposited on Rh nanoparticles. The synthesized electrocatalysts were characterized by TEM and XRD. The reaction products were monitored by on-line DEMS experiments. Potentiodynamic curves showed higher overall reaction rate for Pt/C when compared to that for Rh/C. However, on-line DEMS measurements revealed higher average current efficiencies for complete ethanol electro-oxidation to CO2 on Rh/C. The average current efficiencies for CO2 formation increased with temperature and with the decrease in the ethanol concentration. The total amount of CO2, on the other hand, was slightly affected by the temperature and ethanol concentration. Additionally, the CO2 signal was observed only in the positive-going scan, none being observed in the negative-going scan, evidencing that the C-C bond breaking occurs only at lower potentials. Thus, the formation of CO2 mainly resulted from oxidative removal of adsorbed CO and CHx,ad species generated at the lower potentials, instead of the electrochemical oxidation of bulk ethanol molecules. The acetaldehyde mass signal, however, was greatly favored after increasing the ethanol concentration from 0.01 to 0.1 mol L-1, on both electrocatalysts, indicating that it is the major reaction product. For the Pt/Rh/C-based electrocatalysts, the Faradaic current and the conversion efficiency for CO2 formation was increased by adjusting the amount of Pt on the surface of the Rh/C nanoparticles. The higher conversion efficiency for CO2 formation on the Pt1Rh/C material was ascribed to its faster and more extensive ethanol deprotonation on the Pt-Rh sites, producing adsorbed intermediates in which the C-C bond cleavage is facilitated. (C) 2012 Elsevier B.V. All rights reserved.

On-line mass spectrometry of the electro-oxidation of methanol in acidic media on tungsten carbide

The electro-oxidation of methanol at supported tungsten carbide (WC) nanoparticles in sulfuric acid solution was studied using cyclic voltammetry, potentiostatic measurements, and differential electrochemical mass spectroscopy (DEMS). The catalyst was prepared by a sonochemical method and characterized by X-ray diffraction. Over the WC catalyst, the oxidation of methanol (1 M in a sulfuric acid electrolyte) begins at a potential below 0.5 V/RHE during the anodic sweep. During potentiostatic measurements, a maximum current of 0.8 mA mg(-1) was obtained at 0.4 V. Measurements of DEMS showed that the methanol oxidation reaction over tungsten carbide produces CO2 (m/z=44); no methylformate (m/z=60) was detected. These results are discussed in the context of the continued search for alternative materials for the anode catalyst of direct methanol fuel cells.

Proposta educacional on-line sobre úlcera por pressão para alunos e profissionais de enfermagem

OBJETIVOS: Desenvolver uma proposta educacional on-line sobre o tema úlcera por pressão para alunos e profissionais de enfermagem. MÉTODOS: Pesquisa aplicada, de produção tecnológica, composta pelas etapas de concepção/ planejamento e desenvolvimento, caracterizadas por um conjunto de procedimentos, documentação, digitalização de informações e de imagens. Foram utilizados recursos computacionais didáticos interativos como: o Cybertutor e o Homem Virtual. RESULTADOS: Desenvolvimento de uma proposta educacional virtual sobre úlcera por pressão (UP) dividida em módulos de aprendizagem, contendo lista de discussão, estudos de casos e recursos didáticos, tais como fotos e o Homem Virtual. CONCLUSÕES: Utilizou-se de novas tecnologias educacionais, com a finalidade de promover o aprendizado sobre UP a estudantes de graduação de enfermagem e possibilitar a educação continuada de enfermeiros, uma vez que as UP representam um desafio aos profissionais da saúde e aos serviços de saúde.

On-line identification of minor flavones from sugarcane juice by LC/UV/MS and post-column derivatization

This work describes the on-line characterization of minor flavones from sugarcane (Saccharum officinarum) juice by high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry (LC/UV/MS) using atmospheric pressure chemical ionization-collision-induced dissociation (APCI-CID-MS/MS) and post-column derivatization using UV shift reagents. HPLC-UV analysis with shift reagents provided information about the substitution pattern in the flavonoid skeleton and, combined with MS data, these techniques allowed for the on-line identification of five "garapa" flavones: luteolin-8-C-glucosyl-7-O-glucuronide; tricin-7-O-neohesperoside-4'-O-rhamnoside; tricin-7-O-methylglucuronate-4'-O-rhamnoside; tricin-7-O-methylglucuronide; swertisin, while four other compounds were partially identified as glycosylflavones. Only swertisin (7-O-methylapigenin-6-C-glucoside) was reported previously in sugarcane molasses.

Exploitation of a single interface flow system for on-line aqueous biphasic extraction

The exploitation of aqueous biphasic extraction is proposed for the first time in flow analysis This extraction strategy stands out for being environmentally attractive since it is based in the utilization of two immiscible phases that are intrinsically aqueous The organic solvents of the traditional liquid-liquid extractions ale no longer used, being replaced by non-toxic, non-flammable and non-volatile ones. A single interface flow analysis (SIFA) system was implemented to carry out the extraction process due to its favourable operational characteristics that include the high automation level and simplicity of operation, the establishment of a dynamic interface where the mass transfer occurred between the two immiscible aqueous phases, and the versatile control over the extraction process namely the extraction time The application selected to demonstrate the feasibility of SIFA to perform this aqueous biphasic extraction was the pre-concentration of lead. After extraction, lead reacted with 8-hydroxyquinoline-5-sulfonic acid and the resulting product was determined by a fluorimetric detector included in the flow manifold. Therefore, the SIFA single interface was used both as extraction (enrichment) and reaction interface. (C) 2010 Elsevier B.V All rights reserved.

On-line fault diagnostic system for proton exchange membrane fuel cells

In this paper, a supervisor system, able to diagnose different types of faults during the operation of a proton exchange membrane fuel cell is introduced. The diagnosis is developed by applying Bayesian networks, which qualify and quantify the cause-effect relationship among the variables of the process. The fault diagnosis is based on the on-line monitoring of variables easy to measure in the machine such as voltage, electric current, and temperature. The equipment is a fuel cell system which can operate even when a fault occurs. The fault effects are based on experiments on the fault tolerant fuel cell, which are reproduced in a fuel cell model. A database of fault records is constructed from the fuel cell model, improving the generation time and avoiding permanent damage to the equipment. (C) 2007 Elsevier B.V. All rights reserved.

Diagnostic errors and repetitive sequential classifications in on-line process control by attributes

The procedure of on-line process control by attributes, known as Taguchi`s on-line process control, consists of inspecting the mth item (a single item) at every m produced items and deciding, at each inspection, whether the fraction of conforming items was reduced or not. If the inspected item is nonconforming, the production is stopped for adjustment. As the inspection system can be subject to diagnosis errors, one develops a probabilistic model that classifies repeatedly the examined item until a conforming or b non-conforming classification is observed. The first event that occurs (a conforming classifications or b non-conforming classifications) determines the final classification of the examined item. Proprieties of an ergodic Markov chain were used to get the expression of average cost of the system of control, which can be optimized by three parameters: the sampling interval of the inspections (m); the number of repeated conforming classifications (a); and the number of repeated non-conforming classifications (b). The optimum design is compared with two alternative approaches: the first one consists of a simple preventive policy. The production system is adjusted at every n produced items (no inspection is performed). The second classifies the examined item repeatedly r (fixed) times and considers it conforming if most classification results are conforming. Results indicate that the current proposal performs better than the procedure that fixes the number of repeated classifications and classifies the examined item as conforming if most classifications were conforming. On the other hand, the preventive policy can be averagely the most economical alternative rather than those ones that require inspection depending on the degree of errors and costs. A numerical example illustrates the proposed procedure. (C) 2009 Elsevier B. V. All rights reserved.

A dynamic model with on-line identification for rotary sugar drying processes

A dynamic modelling methodology, which combines on-line variable estimation and parameter identification with physical laws to form an adaptive model for rotary sugar drying processes, is developed in this paper. In contrast to the conventional rate-based models using empirical transfer coefficients, the heat and mass transfer rates are estimated by using on-line measurements in the new model. Furthermore, a set of improved sectional solid transport equations with localized parameters is developed in this work to reidentified on-line using measurement data, the model is able to closely track the dynamic behaviour of rotary drying processes within a broad range of operational conditions. This adaptive model is validated against experimental data obtained from a pilot-scale rotary sugar dryer. The proposed modelling methodology can be easily incorporated into nonlinear model based control schemes to form a unified modelling and control framework.place the global correlation for the computation of solid retention time. Since a number of key model variables and parameters are identified on-line using measurement data, the model is able to closely track the dynamic behaviour of rotary drying processes within a broad range of operational conditions. This adaptive model is validated against experimental data obtained from a pilot-scale rotary sugar dryer. The proposed modelling methodology can be easily incorporated into nonlinear model based control schemes to form a unified modelling and control framework.