Descrição do movimento da articulação metacarpofalangiana de equinos pela metodologia baseada em videogrametria

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo das propriedades físico-químicas do biodiesel e suas influências na deterioração dos elastômeros aplicados no sistema de injeção dos motores diesel

The biodiesel use has become important due to its renewable character and to reduce environmental impacts during the fuel burning. Theses benefit will be valid if the fuel shows good performance, chemistry stability and compatibility with engines. Biodiesel is a good fuel to diesel engines due to its lubricity. Then, the aimed of this study was to verify the physicalchemistry properties of biodiesel and their correlations with possible elastomers damage after biodiesel be used as fuel in an injection system. The methodology was divided in three steps: biodiesels synthesis by transesterification of three vegetable oil (soybean, palm and sunflower) and their physical-chemistry characterization (viscosity, oxidative stability, flash point, acidity, humidity and density); pressurized test of compatibility between elastomers (NBR and VITON) and biodiesel, and the last one, analyze of biodiesels lubricity by tribological test ball-plan( HFRR). Also, the effect of mixture of biodiesel and diesel in different concentrations was evaluated. The results showed that VITON showed better compatibility with all biodiesel blends in relation to NBR, however when VITON had contact with sunflower biodiesel and its blends the swelling degree suffer higher influences due to biodiesel humidity. For others biodiesels and theirs blends, this elastomer kept its mechanical properties constant. The better tribological performance was observed for blends with high biodiesel concentration, lower friction coefficient was obtained when palm biodiesel was used. The main mechanisms observed during the HFRR tests were abrasive and oxidative wear

Sistema de injeção em fluxo espectrofotométrico para monitorar peróxido de hidrogênio em processo de fotodegradação por reação foto-Fenton

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

Análise cinemática tridimensional do movimento de eqüinos em esteira rolante

Adaptou-se uma metodologia utilizada no estudo do movimento humano para analisar o movimento de eqüinos em esteira rolante de alto desempenho, construindo-se um sistema de calibração utilizando-se um teodolito eletrônico de alta precisão e calibradores que demarcavam o espaço ocupado pelo animal. Dessa forma, foram obtidas as coordenadas espaciais dos marcadores presentes nos calibradores, compondo o arquivo de calibração. Duas câmeras de vídeo (60Hz) foram posicionadas em vista lateral esquerda, distantes 5m da manta de rolagem da esteira a 1,8m de altura. As imagens foram enquadradas utilizando-se um monitor de vídeo. Para a validação do método, um membro da equipe movimentou, no espaço calibrado, uma haste rígida com marcadores fixados nas suas extremidades, distantes um do outro 43,8cm. Para a análise das imagens, utilizou-se o programa Dvideow, desenvolvido pelo Laboratório de Instrumentação para Biomecânica - UNICAMP. Após a reconstrução tridimensional das imagens utilizou-se um programa matemático para o cálculo do valor médio da distância entre os marcadores. Obteve-se, após a mensuração em 100 quadros, o valor médio de 43,7cm com coeficiente de variação de 0,8%. Estes resultados mostram que a metodologia desenvolvida é precisa e adequada para o estudo da locomoção de eqüinos.

Use of FIA systems for on-line dilution in multielement determination by ICP-MS

A flow-injection (FI) system to match concentrations was used as an auto-diluter in multielement determination by inductively coupled plasma-mass spectrometry (ICP-MS). The flow system comprised loop-based injection or a timed valve that introduced a variable sample volume info a spray chamber through a standard Meinhard nebulizer of an ICP-MS. Routinely analyzed samples such as water, plant, and steel were selected. The accuracy of multielement determination was checked against water standard reference material from the National Institute of Standards and Technology (1643d), plant standard reference material from the National Bureau of Standards (1572 citrus leaves), and steel standard reference material from the National Bureau of Standards (AISI 4340). The measuring system was calibrated with a multielement solution, yielding a linear plot with good precision [relative standard deviation (RSD) < 3%, n = 12]. The results were in agreement at a 95% confidence level with the certified values for the reference materials and also with those obtained by continuous aspiration and by (FI) with a discrete volume. (C) 1999 John Wiley & Sons, Inc.

Development and application of a highly selective biomimetic sensor for detection of captopril, an important ally in hypertension control

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

Desenvolvimento de dispositivos computacionais para registro de dados pluviométricos e análise operacional de pluviômetros basculantes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

High precision astrometry mission for the detection and characterization of nearby habitable planetary systems with the Nearby Earth Astrometric Telescope (NEAT)

A complete census of planetary systems around a volume-limited sample of solar-type stars (FGK dwarfs) in the Solar neighborhood (d a parts per thousand currency signaEuro parts per thousand 15 pc) with uniform sensitivity down to Earth-mass planets within their Habitable Zones out to several AUs would be a major milestone in extrasolar planets astrophysics. This fundamental goal can be achieved with a mission concept such as NEAT-the Nearby Earth Astrometric Telescope. NEAT is designed to carry out space-borne extremely-high-precision astrometric measurements at the 0.05 mu as (1 sigma) accuracy level, sufficient to detect dynamical effects due to orbiting planets of mass even lower than Earth's around the nearest stars. Such a survey mission would provide the actual planetary masses and the full orbital geometry for all the components of the detected planetary systems down to the Earth-mass limit. The NEAT performance limits can be achieved by carrying out differential astrometry between the targets and a set of suitable reference stars in the field. The NEAT instrument design consists of an off-axis parabola single-mirror telescope (D = 1 m), a detector with a large field of view located 40 m away from the telescope and made of 8 small movable CCDs located around a fixed central CCD, and an interferometric calibration system monitoring dynamical Young's fringes originating from metrology fibers located at the primary mirror. The mission profile is driven by the fact that the two main modules of the payload, the telescope and the focal plane, must be located 40 m away leading to the choice of a formation flying option as the reference mission, and of a deployable boom option as an alternative choice. The proposed mission architecture relies on the use of two satellites, of about 700 kg each, operating at L2 for 5 years, flying in formation and offering a capability of more than 20,000 reconfigurations. The two satellites will be launched in a stacked configuration using a Soyuz ST launch vehicle. The NEAT primary science program will encompass an astrometric survey of our 200 closest F-, G- and K-type stellar neighbors, with an average of 50 visits each distributed over the nominal mission duration. The main survey operation will use approximately 70% of the mission lifetime. The remaining 30% of NEAT observing time might be allocated, for example, to improve the characterization of the architecture of selected planetary systems around nearby targets of specific interest (low-mass stars, young stars, etc.) discovered by Gaia, ground-based high-precision radial-velocity surveys, and other programs. With its exquisite, surgical astrometric precision, NEAT holds the promise to provide the first thorough census for Earth-mass planets around stars in the immediate vicinity of our Sun.

Tools and methods for the quality assurance of force platforms in human movement analysis

The human movement analysis (HMA) aims to measure the abilities of a subject to stand or to walk. In the field of HMA, tests are daily performed in research laboratories, hospitals and clinics, aiming to diagnose a disease, distinguish between disease entities, monitor the progress of a treatment and predict the outcome of an intervention [Brand and Crowninshield, 1981; Brand, 1987; Baker, 2006]. To achieve these purposes, clinicians and researchers use measurement devices, like force platforms, stereophotogrammetric systems, accelerometers, baropodometric insoles, etc. This thesis focus on the force platform (FP) and in particular on the quality assessment of the FP data. The principal objective of our work was the design and the experimental validation of a portable system for the in situ calibration of FPs. The thesis is structured as follows: Chapter 1. Description of the physical principles used for the functioning of a FP: how these principles are used to create force transducers, such as strain gauges and piezoelectrics transducers. Then, description of the two category of FPs, three- and six-component, the signals acquisition (hardware structure), and the signals calibration. Finally, a brief description of the use of FPs in HMA, for balance or gait analysis. Chapter 2. Description of the inverse dynamics, the most common method used in the field of HMA. This method uses the signals measured by a FP to estimate kinetic quantities, such as joint forces and moments. The measures of these variables can not be taken directly, unless very invasive techniques; consequently these variables can only be estimated using indirect techniques, as the inverse dynamics. Finally, a brief description of the sources of error, present in the gait analysis. Chapter 3. State of the art in the FP calibration. The selected literature is divided in sections, each section describes: systems for the periodic control of the FP accuracy; systems for the error reduction in the FP signals; systems and procedures for the construction of a FP. In particular is detailed described a calibration system designed by our group, based on the theoretical method proposed by ?. This system was the “starting point” for the new system presented in this thesis. Chapter 4. Description of the new system, divided in its parts: 1) the algorithm; 2) the device; and 3) the calibration procedure, for the correct performing of the calibration process. The algorithm characteristics were optimized by a simulation approach, the results are here presented. In addiction, the different versions of the device are described. Chapter 5. Experimental validation of the new system, achieved by testing it on 4 commercial FPs. The effectiveness of the calibration was verified by measuring, before and after calibration, the accuracy of the FPs in measuring the center of pressure of an applied force. The new system can estimate local and global calibration matrices; by local and global calibration matrices, the non–linearity of the FPs was quantified and locally compensated. Further, a non–linear calibration is proposed. This calibration compensates the non– linear effect in the FP functioning, due to the bending of its upper plate. The experimental results are presented. Chapter 6. Influence of the FP calibration on the estimation of kinetic quantities, with the inverse dynamics approach. Chapter 7. The conclusions of this thesis are presented: need of a calibration of FPs and consequential enhancement in the kinetic data quality. Appendix: Calibration of the LC used in the presented system. Different calibration set–up of a 3D force transducer are presented, and is proposed the optimal set–up, with particular attention to the compensation of non–linearities. The optimal set–up is verified by experimental results.

Numerical simulations of magma chamber dynamics at Campi Flegrei, and associated seismicity, deformation and gravity changes

Understanding the complex relationships between quantities measured by volcanic monitoring network and shallow magma processes is a crucial headway for the comprehension of volcanic processes and a more realistic evaluation of the associated hazard. This question is very relevant at Campi Flegrei, a volcanic quiescent caldera immediately north-west of Napoli (Italy). The system activity shows a high fumarole release and periodic ground slow movement (bradyseism) with high seismicity. This activity, with the high people density and the presence of military and industrial buildings, makes Campi Flegrei one of the areas with higher volcanic hazard in the world. In such a context my thesis has been focused on magma dynamics due to the refilling of shallow magma chambers, and on the geophysical signals detectable by seismic, deformative and gravimetric monitoring networks that are associated with this phenomenologies. Indeed, the refilling of magma chambers is a process frequently occurring just before a volcanic eruption; therefore, the faculty of identifying this dynamics by means of recorded signal analysis is important to evaluate the short term volcanic hazard. The space-time evolution of dynamics due to injection of new magma in the magma chamber has been studied performing numerical simulations with, and implementing additional features in, the code GALES (Longo et al., 2006), recently developed and still on the upgrade at the Istituto Nazionale di Geofisica e Vulcanologia in Pisa (Italy). GALES is a finite element code based on a physico-mathematical two dimensional, transient model able to treat fluids as multiphase homogeneous mixtures, compressible to incompressible. The fundamental equations of mass, momentum and energy balance are discretised both in time and space using the Galerkin Least-Squares and discontinuity-capturing stabilisation technique. The physical properties of the mixture are computed as a function of local conditions of magma composition, pressure and temperature.The model features enable to study a broad range of phenomenologies characterizing pre and sin-eruptive magma dynamics in a wide domain from the volcanic crater to deep magma feeding zones. The study of displacement field associated with the simulated fluid dynamics has been carried out with a numerical code developed by the Geophysical group at the University College Dublin (O’Brien and Bean, 2004b), with whom we started a very profitable collaboration. In this code, the seismic wave propagation in heterogeneous media with free surface (e.g. the Earth’s surface) is simulated using a discrete elastic lattice where particle interactions are controlled by the Hooke’s law. This method allows to consider medium heterogeneities and complex topography. The initial and boundary conditions for the simulations have been defined within a coordinate project (INGV-DPC 2004-06 V3_2 “Research on active volcanoes, precursors, scenarios, hazard and risk - Campi Flegrei”), to which this thesis contributes, and many researchers experienced on Campi Flegrei in volcanological, seismic, petrological, geochemical fields, etc. collaborate. Numerical simulations of magma and rock dynamis have been coupled as described in the thesis. The first part of the thesis consists of a parametric study aimed at understanding the eect of the presence in magma of carbon dioxide in magma in the convection dynamics. Indeed, the presence of this volatile was relevant in many Campi Flegrei eruptions, including some eruptions commonly considered as reference for a future activity of this volcano. A set of simulations considering an elliptical magma chamber, compositionally uniform, refilled from below by a magma with volatile content equal or dierent from that of the resident magma has been performed. To do this, a multicomponent non-ideal magma saturation model (Papale et al., 2006) that considers the simultaneous presence of CO2 and H2O, has been implemented in GALES. Results show that the presence of CO2 in the incoming magma increases its buoyancy force promoting convection ad mixing. The simulated dynamics produce pressure transients with frequency and amplitude in the sensitivity range of modern geophysical monitoring networks such as the one installed at Campi Flegrei . In the second part, simulations more related with the Campi Flegrei volcanic system have been performed. The simulated system has been defined on the basis of conditions consistent with the bulk of knowledge of Campi Flegrei and in particular of the Agnano-Monte Spina eruption (4100 B.P.), commonly considered as reference for a future high intensity eruption in this area. The magmatic system has been modelled as a long dyke refilling a small shallow magma chamber; magmas with trachytic and phonolitic composition and variable volatile content of H2O and CO2 have been considered. The simulations have been carried out changing the condition of magma injection, the system configuration (magma chamber geometry, dyke size) and the resident and refilling magma composition and volatile content, in order to study the influence of these factors on the simulated dynamics. Simulation results allow to follow each step of the gas-rich magma ascent in the denser magma, highlighting the details of magma convection and mixing. In particular, the presence of more CO2 in the deep magma results in more ecient and faster dynamics. Through this simulations the variation of the gravimetric field has been determined. Afterward, the space-time distribution of stress resulting from numerical simulations have been used as boundary conditions for the simulations of the displacement field imposed by the magmatic dynamics on rocks. The properties of the simulated domain (rock density, P and S wave velocities) have been based on data from literature on active and passive tomographic experiments, obtained through a collaboration with A. Zollo at the Dept. of Physics of the Federici II Univeristy in Napoli. The elasto-dynamics simulations allow to determine the variations of the space-time distribution of deformation and the seismic signal associated with the studied magmatic dynamics. In particular, results show that these dynamics induce deformations similar to those measured at Campi Flegrei and seismic signals with energies concentrated on the typical frequency bands observed in volcanic areas. The present work shows that an approach based on the solution of equations describing the physics of processes within a magmatic fluid and the surrounding rock system is able to recognise and describe the relationships between geophysical signals detectable on the surface and deep magma dynamics. Therefore, the results suggest that the combined study of geophysical data and informations from numerical simulations can allow in a near future a more ecient evaluation of the short term volcanic hazard.

The new Beam Halo Monitor for the CMS experiment at the LHC

In the context of increasing beam energy and luminosity of the LHC accelerator at CERN, it will be important to accurately measure the Machine Induced Background. A new monitoring system will be installed in the CMS cavern for measuring the beam background at high radius. This detector, called the Beam Halo Monitor, will provide an online, bunch-by-bunch measurement of background induced by beam halo interactions, separately for each beam. The detector is composed of synthetic quartz Cherenkov radiators, coupled to fast UV sensitive photomultiplier tubes. The directional and fast response of the system allows the discrimination of the background particles from the dominant flux in the cavern induced by pp collision debris, produced within the 25 ns bunch spacing. The readout electronics of this detector will make use of many components developed for the upgrade of the CMS Hadron Calorimeter electronics, with a dedicated firmware and readout adapted to the beam monitoring requirements. The PMT signal will be digitized by a charge integrating ASIC, providing both the signal rise time and the charge integrated over one bunch crossing. The backend electronics will record bunch-by-bunch histograms, which will be published to CMS and the LHC using the newly designed CMS beam instrumentation specific DAQ. A calibration and monitoring system has been designed to generate triggered pulses of UV light to monitor the efficiency of the system. The experimental results validating the design of the detector, the calibration system and the electronics will be presented.

Técnicas de procesado digital de señal aplicadas a acelerómetros

En este proyecto se estudian y analizan las diferentes técnicas de procesado digital de señal aplicadas a acelerómetros. Se hace uso de una tarjeta de prototipado, basada en DSP, para realizar las diferentes pruebas. El proyecto se basa, principalmente, en realizar filtrado digital en señales provenientes de un acelerómetro en concreto, el 1201F, cuyo campo de aplicación es básicamente la automoción. Una vez estudiadas la teoría de procesado y las características de los filtros, diseñamos una aplicación basándonos sobre todo en el entorno en el que se desarrollaría una aplicación de este tipo. A lo largo del diseño, se explican las diferentes fases: diseño por ordenador (Matlab), diseño de los filtros en el DSP (C), pruebas sobre el DSP sin el acelerómetro, calibración del acelerómetro, pruebas finales sobre el acelerómetro... Las herramientas utilizadas son: la plataforma Kit de evaluación 21-161N de Analog Devices (equipado con el entorno de desarrollo Visual DSP 4.5++), el acelerómetro 1201F, el sistema de calibración de acelerómetros CS-18-LF de Spektra y los programas software MATLAB 7.5 y CoolEditPRO 2.0. Se realizan únicamente filtros IIR de 2º orden, de todos los tipos (Butterworth, Chebyshev I y II y Elípticos). Realizamos filtros de banda estrecha, paso-banda y banda eliminada, de varios tipos, dentro del fondo de escala que permite el acelerómetro. Una vez realizadas todas las pruebas, tanto simulaciones como físicas, se seleccionan los filtros que presentan un mejor funcionamiento y se analizan para obtener conclusiones. Como se dispone de un entorno adecuado para ello, se combinan los filtros entre sí de varias maneras, para obtener filtros de mayor orden (estructura paralelo). De esta forma, a partir de filtros paso-banda, podemos obtener otras configuraciones que nos darán mayor flexibilidad. El objetivo de este proyecto no se basa sólo en obtener buenos resultados en el filtrado, sino también de aprovechar las facilidades del entorno y las herramientas de las que disponemos para realizar el diseño más eficiente posible. In this project, we study and analize digital signal processing in order to design an accelerometer-based application. We use a hardware card of evaluation, based on DSP, to make different tests. This project is based in design digital filters for an automotion application. The accelerometer type is 1201F. First, we study digital processing theory and main parameters of real filters, to make a design based on the application environment. Along the application, we comment all the different steps: computer design (Matlab), filter design on the DSP (C language), simulation test on the DSP without the accelerometer, accelerometer calibration, final tests on the accelerometer... Hardware and software tools used are: Kit of Evaluation 21-161-N, based on DSP, of Analog Devices (equiped with software development tool Visual DSP 4.5++), 1201-F accelerometer, CS-18-LF calibration system of SPEKTRA and software tools MATLAB 7.5 and CoolEditPRO 2.0. We only perform 2nd orden IIR filters, all-type : Butterworth, Chebyshev I and II and Ellyptics. We perform bandpass and stopband filters, with very narrow band, taking advantage of the accelerometer's full scale. Once all the evidence, both simulations and physical, are finished, filters having better performance and analyzed and selected to draw conclusions. As there is a suitable environment for it, the filters are combined together in different ways to obtain higher order filters (parallel structure). Thus, from band-pass filters, we can obtain many configurations that will give us greater flexibility. The purpose of this project is not only based on good results in filtering, but also to exploit the facilities of the environment and the available tools to make the most efficient design possible.

Determinação a baixo custo de açúcares redutores totais em caldo-de-cana, empregando sistemas de análise por injeção em fluxo com o uso de DNS

Determinação a baixo custo de açúcares redutores totais em caldo-de-cana, empregando sistema de análise por injeção em fluxo com o uso de DNS Um sistema de análise por injeção em fluxo foi utilizado para a determinação de açúcares redutores totais em caldo-de-cana. O método é baseado na hidrólise da sacarose, seguido da oxidação dos açúcares redutores pelo ácido 3,5-dinitrosalicílico (DNS) em meio alcalino, e determinação espectrofotométrica em 510 nm. Visando obter melhor sensibilidade e seletividade, os parâmetros volume de amostra e comprimento dos reatores foram estudados para avaliar o comportamento das curvas analíticas. Foram utilizados mini-compressores de aquários no lugar de bomba peristálticas e cela espectrofotométrica em acrílico no lugar de cela de vidro importada, a fim de minimizar o consumo de reagentes e o custo do sistema FIA. O presente sistema foi comparado ao método Lane-Eynon recomendado pelo Ministério da Agricultura. Usando o teste-t, não foram constatadas diferenças significativas entre os resultados dos dois métodos, sendo que os desvios relativos foram ao redor de 1%. O método permite analisar cerca de 14 amostras h-1 com desvio padrão relativo inferior a 1,35%.

On precise three-dimensional environment modeling via UAV-based photogrammetric systems

Abstract : Images acquired from unmanned aerial vehicles (UAVs) can provide data with unprecedented spatial and temporal resolution for three-dimensional (3D) modeling. Solutions developed for this purpose are mainly operating based on photogrammetry concepts, namely UAV-Photogrammetry Systems (UAV-PS). Such systems are used in applications where both geospatial and visual information of the environment is required. These applications include, but are not limited to, natural resource management such as precision agriculture, military and police-related services such as traffic-law enforcement, precision engineering such as infrastructure inspection, and health services such as epidemic emergency management. UAV-photogrammetry systems can be differentiated based on their spatial characteristics in terms of accuracy and resolution. That is some applications, such as precision engineering, require high-resolution and high-accuracy information of the environment (e.g. 3D modeling with less than one centimeter accuracy and resolution). In other applications, lower levels of accuracy might be sufficient, (e.g. wildlife management needing few decimeters of resolution). However, even in those applications, the specific characteristics of UAV-PSs should be well considered in the steps of both system development and application in order to yield satisfying results. In this regard, this thesis presents a comprehensive review of the applications of unmanned aerial imagery, where the objective was to determine the challenges that remote-sensing applications of UAV systems currently face. This review also allowed recognizing the specific characteristics and requirements of UAV-PSs, which are mostly ignored or not thoroughly assessed in recent studies. Accordingly, the focus of the first part of this thesis is on exploring the methodological and experimental aspects of implementing a UAV-PS. The developed system was extensively evaluated for precise modeling of an open-pit gravel mine and performing volumetric-change measurements. This application was selected for two main reasons. Firstly, this case study provided a challenging environment for 3D modeling, in terms of scale changes, terrain relief variations as well as structure and texture diversities. Secondly, open-pit-mine monitoring demands high levels of accuracy, which justifies our efforts to improve the developed UAV-PS to its maximum capacities. The hardware of the system consisted of an electric-powered helicopter, a high-resolution digital camera, and an inertial navigation system. The software of the system included the in-house programs specifically designed for camera calibration, platform calibration, system integration, onboard data acquisition, flight planning and ground control point (GCP) detection. The detailed features of the system are discussed in the thesis, and solutions are proposed in order to enhance the system and its photogrammetric outputs. The accuracy of the results was evaluated under various mapping conditions, including direct georeferencing and indirect georeferencing with different numbers, distributions and types of ground control points. Additionally, the effects of imaging configuration and network stability on modeling accuracy were assessed. The second part of this thesis concentrates on improving the techniques of sparse and dense reconstruction. The proposed solutions are alternatives to traditional aerial photogrammetry techniques, properly adapted to specific characteristics of unmanned, low-altitude imagery. Firstly, a method was developed for robust sparse matching and epipolar-geometry estimation. The main achievement of this method was its capacity to handle a very high percentage of outliers (errors among corresponding points) with remarkable computational efficiency (compared to the state-of-the-art techniques). Secondly, a block bundle adjustment (BBA) strategy was proposed based on the integration of intrinsic camera calibration parameters as pseudo-observations to Gauss-Helmert model. The principal advantage of this strategy was controlling the adverse effect of unstable imaging networks and noisy image observations on the accuracy of self-calibration. The sparse implementation of this strategy was also performed, which allowed its application to data sets containing a lot of tie points. Finally, the concepts of intrinsic curves were revisited for dense stereo matching. The proposed technique could achieve a high level of accuracy and efficiency by searching only through a small fraction of the whole disparity search space as well as internally handling occlusions and matching ambiguities. These photogrammetric solutions were extensively tested using synthetic data, close-range images and the images acquired from the gravel-pit mine. Achieving absolute 3D mapping accuracy of 11±7 mm illustrated the success of this system for high-precision modeling of the environment.

Sequential injections as an alternative to gradient exploitation for implementing differential kinetic analysis in a flow injection system

A novel flow-based strategy for implementing simultaneous determinations of different chemical species reacting with the same reagent(s) at different rates is proposed and applied to the spectrophotometric catalytic determination of iron and vanadium in Fe-V alloys. The method relies on the influence of Fe(II) and V(IV) on the rate of the iodide oxidation by Cr(VI) under acidic conditions, the Jones reducing agent is then needed Three different plugs of the sample are sequentially inserted into an acidic KI reagent carrier stream, and a confluent Cr(VI) solution is added downstream Overlap between the inserted plugs leads to a complex sample zone with several regions of maximal and minimal absorbance values. Measurements performed on these regions reveal the different degrees of reaction development and tend to be more precise Data are treated by multivariate calibration involving the PLS algorithm The proposed system is very simple and rugged Two latent variables carried out ca 95% of the analytical information and the results are in agreement with ICP-OES. (C) 2010 Elsevier B V. All rights reserved.