Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

Pulsatile Blood Flow Simulations in Computed Tomography(CT) Scan-Based and Idealized Geometries of Human Aorta

Blood flow in human aorta is an unsteady and complex phenomenon. The complex patterns are related to the geometrical features like curvature, bends, and branching and pulsatile nature of flow from left ventricle of heart. The aim of this work was to understand the effect of aorta geometry on the flow dynamics. To achieve this, 3D realistic and idealized models of descending aorta were reconstructed from Computed Tomography (CT) images of a female patient. The geometries were reconstructed using medical image processing code. The blood flow in aorta was assumed to be laminar and incompressible and the blood was assumed to be Newtonian fluid. A time dependent pulsatile and parabolic boundary condition was deployed at inlet. Steady and unsteady blood flow simulations were performed in real and idealized geometries of descending aorta using a Finite Volume Method (FVM) code. Analysis of Wall Shear Stress (WSS) distribution, pressure distribution, and axial velocity profiles were carried out in both geometries at steady and unsteady state conditions. The results obtained in thesis work reveal that the idealization of geometry underestimates the values of WSS especially near the region with sudden change of diameter. However, the resultant pressure and velocity in idealized geometry are close to those in real geometry

Simulating Fluid Flow in a Compressed Valve

The objective of the work is to study fluid flow behavior through a pinch valve and to estimate the flow coefficient (KV ) at different opening positions of the valve. The flow inside a compressed valve is more complex than in a straight pipe, and it is one of main topics of interest for engineers in process industry. In the present work, we have numerically simulated compressed valve flow at different opening positions. In order to simulate the flow through pinch valve, several models of the elastomeric valve tube (pinch valve tube) at different opening positions were constructed in 2D-axisymmetric and 3D geometries. The numerical simulations were performed with the CFD packages; ANSYS FLUENT and ANSYS CFX by using parallel computing. The distributions of static pressure, velocity and turbulent kinetic energy have been studied at different opening positions of the valve in both 2D-axisymmetric and 3D experiments. The flow coefficient (KV ) values have been measured at different valve openings and are compared between 2D-axisymmetric and 3D simulation results.

Numerical Investigation of Flow Past a Circular Cylinder and in a Staggered Tube Bundle Using Various Turbulence Models

Transitional flow past a three-dimensional circular cylinder is a widely studied phenomenon since this problem is of interest with respect to many technical applications. In the present work, the numerical simulation of flow past a circular cylinder, performed by using a commercial CFD code (ANSYS Fluent 12.1) with large eddy simulation (LES) and RANS (κ - ε and Shear-Stress Transport (SST) κ - ω! model) approaches. The turbulent flow for ReD = 1000 & 3900 is simulated to investigate the force coefficient, Strouhal number, flow separation angle, pressure distribution on cylinder and the complex three dimensional vortex shedding of the cylinder wake region. The numerical results extracted from these simulations have good agreement with the experimental data (Zdravkovich, 1997). Moreover, grid refinement and time-step influence have been examined. Numerical calculations of turbulent cross-flow in a staggered tube bundle continues to attract interest due to its importance in the engineering application as well as the fact that this complex flow represents a challenging problem for CFD. In the present work a time dependent simulation using κ – ε, κ - ω! and SST models are performed in two dimensional for a subcritical flow through a staggered tube bundle. The predicted turbulence statistics (mean and r.m.s velocities) have good agreement with the experimental data (S. Balabani, 1996). Turbulent quantities such as turbulent kinetic energy and dissipation rate are predicted using RANS models and compared with each other. The sensitivity of grid and time-step size have been analyzed. Model constants sensitivity study have been carried out by adopting κ – ε model. It has been observed that model constants are very sensitive to turbulence statistics and turbulent quantities.

Spectrophotometric flow injection procedure to indirect determination of paracetamol in pharmaceutical formulations using o-tolidine as reagent

A spectrophotometric flow injection method for the determination of paracetamol in pharmaceutical formulations is proposed. The procedure was based on the oxidation of paracetamol by sodium hypochloride and the determination of the excess of this oxidant using o-tolidine dichloride as chromogenic reagent at 430 nm. The analytical curve was linear in the paracetamol concentration range from 8.50 x 10-6 to 2.51 x 10-4 mol L-1 with a detection limit of 5.0 x 10-6 mol L-1. The relative standard deviation was smaller than 1.2% for 1.20 x 10-4 mol L-1 paracetamol solution (n = 10). The results obtained for paracetamol in pharmaceutical formulations using the proposed flow injection method and those obtained using a USP Pharmacopoeia method are in agreement at the 95% confidence level.

Flow injection analysis of vancomycin

A flow injection method for the quantitative analysis of vancomycin hydrochloride, C66H75Cl2N9O24.HCl (HVCM), based on the reaction with copper (II) ions, is presented. HVCM forms a lilac-blue complex with copper ions at pH≅4.5 in aqueous solutions, with maximum absorption at 555 nm. The detection limit was estimated to be about 8.5×10-5 mol L-1; the quantitation limit is about 2.5×10-4 mol L-1 and about 30 determinations can be performed in an hour. The accuracy of the method was tested through recovery procedures in presence of four different excipients, in the proportion 1:1 w/w. The results were compared with those obtained with the batch spectrophotometric and with the HPLC methods. Statistical comparison was done using the Student's procedure. Complete agreement was found at a 0.95 significance level between the proposed flow injection and the batch spectrophotometric methods, which present similar precision (RSD: 2.1 % vs. 1.9%).

Flow injection visible diffuse reflectance quantitative analysis of total sulfur in biodiesel, in plant leaves and in natural waters

Flow injection (FI) methodology, using diffuse reflectance in the visible region of the spectrum, for the analysis of total sulfur in the form of sulfate, precipitated in the form of barium sulfate, is presented. The method was applied to biodiesel, to plant leaves and to natural waters analysis. The analytical signal (S) correlates linearly with sulfate concentration (C) between 20 and 120 ppm, through the equation S=-1.138+0.0934 C (r = 0.9993). The experimentally observed limit of detection is about 10 ppm. The mean R.S.D. is about 3.0 %. Real samples containing sulfate were analyzed and the results obtained by the FI and by the reference batch turbidimetric method using the statistical Student's t-test and F-test were compared.

Flow-batch analyser for preparation of calibration standard mixtures in simultaneous multicomponent spectrometric analysis

The application of multivariate calibration techniques to multicomponent analysis by UV-VIS molecular absorption spectrometry is a powerful tool for simultaneous determination of several chemical species. However, when this methodology is accomplished manually, it is slow and laborious, consumes high amounts of reagents and samples, is susceptible to contaminations and presents a high operational cost. To overcome these drawbacks, a flow-batch analyser is proposed in this work. This analyser was developed for automatic preparation of standard calibration and test (or validation) mixtures. It was applied to the simultaneous determination of Cu2+, Mn2+ and Zn2+ in polyvitaminic and polymineral pharmaceutical formulations, using 4-(2-piridilazo) resorcinol as reagent and a UV-VIS spectrophotometer with a photodiode array detector. The results obtained with the proposed system are in good agreement with those obtained by flame atomic absorption spectrometry, which was employed as reference method. With the proposed analyser, the preparation of calibration and test mixtures can be accomplished about four hours, while the manual procedure requires at least two days. Moreover, it consumes smaller amounts of reagents and samples than the manual procedure. After the preparation of calibration and test mixtures, 60 samples h-1 can be carried out with the proposed flow-batch analyser.

Spectrophotometric flow injection system for determination of Zn2+ in ophthalmic formulations using Alizarin red S

A spectrophotometric flow injection method for the determination of Zn(II) in ophthalmic formulations was developed. In this work, Zn(II) ion was complexed with Alizarin red S in borate buffer solution (pH 9.0) and the chromophore produced was monitored at 520 nm. The analytical curve was linear in the Zn(II) concentration range from 6.05 x 10-6 to 1.50 x 10-4 mol L-1 with a detection limit of 3.60 x 10-6 mol L-1. Recoveries ranged from 96.3 to 105 % and a relative standard deviation of 1.2 % (n = 10) for 5.5x10-5 mol L-1 Zn(II) reference solution were obtained. The sampling rate was 60 h-1 and the results obtained of Zn(II) in ophthalmic products using this procedure are in close agreement with those obtained using a comparative spectrophotometric procedure at 95 % confidence level.

Traffic flow development at North European company level with respect of China and Russia

The aim of the thesis is to analyze traffic flows and its development from North European companies` point of view to China and Russia using data from logistics questionnaire. Selected North European companies are large Finnish and Swedish companies. The questionnaire was sent via email to the target group. The study is based on the answers got from respondent companies from years 2006, 2009 and 2010. In the thesis Finnish Talouselämä newspaper and Swedish Affärsdata are used as a database to find the target companies for the survey. Respondents were most often logistics managers in companies. In the beginning of the thesis concepts of transportation logistics is presented, including container types, trade terms, axel loads in roads and in railways. Also there is information about warehousing types and terminals. After that, general information of Chinese and Russian transportation logistics is presented. Chinese and Russian issues are discussed in two sections. In both of them it is analyzed economic development, freight transport and trade balance. Some practical examples of factory inaugurations in China and Russia are presented that Finnish and Swedish companies have completed. In freight transport section different transportation modes, logistics outsourcing and problems of transportation logistics is discussed. The results of the thesis show that transportation flows between Europe and China is changing. Freight traffic from China to European countries will strengthen even more from the current base. When it comes to Russia and Europe, traffic flows seem to be changing from eastbound traffic to westbound traffic. It means that in the future it is expected more freight traffic from Russia to Europe. Some probable reasons for that are recent factory establishments in Russia and company interviews support also this observation. Effects of the economic recession are mainly seen in the lower transportation amounts in 2009.

A pH optode based on thymol blue: application to determination of CO2 using flow injection analysis system

An optode based on thymol blue (TB), an acid-based indicator, has been constructed and evaluated as a detector in FIA system for CO2 determination. The dye was chemically immobilised on the surface of a bifurcated glass optical fibre bundle, using silanisation in organic media. In FIA system, hydrogen carbonate or carbonate samples are injected in a buffer carrier solution, and then are mixed with phosphoric acid solution to generate CO2, which diffuses through a PTFE membrane, in order to be collected in an acceptor carrier fluid, pumped towards to detection cell, in which the optode was adapted. The proposed system presents two linear response ranges, from 1.0 x 10-3 to 1.0 x 10-2 mol l-1, and from 2.0 x 10-2 to 0.10 mol l-1. The sampling frequency was 11 sample h-1, with good repeatability (R.S.D < 4 %, n = 10). In flow conditions the optode lifetime was 170 h. The system was applied in the analysis of commercial mineral water and the results obtained in the hydrogen carbonate determination did not differ significantly from those obtained by potentiometry, at a confidence level of 95 %.

Det var intressant, man måste tänka så mycket : öppna laborationer och V-diagram i kemiundervisningen

Laborationerna utgör i många skolor inom den grundläggande utbildningen en självklar del av kemiundervisningen. Laborationerna är vanligen formulerade som ”recept” och eleverna skall följa en given beskrivning då de genomför laborationen. Kravet på eget tänkande från elevernas sida kan härigenom bli litet. Laborationerna är därför utsatta för en hel del kritik på olika håll i världen, därför att de anses ineffektiva ur lärande-synvinkel. S.k. öppna laborationer är en annan typ av laboration som innebär att eleverna ställs inför ett problem eller en utmaning. Eleverna skall själva inom sin laborationsgrupp komma underfund med och planera hur de skall genomföra laborationen. Denna form av laborationer ställer andra krav på elevernas tänkande än traditionella ”kokbokslaborationer”. I denna studie har elever i en klass i årskurs 7 under sin första kemikurs arbetat med öppna laborationer. Laborationerna har av klassens lärare formulerats som utmaningar för eleverna. Eleverna har som ett hjälpverktyg under laborationen använt s.k. V-diagram. V-diagram utgör ett grafiskt verktyg som kan användas som en laborationsrapport. I V-diagrammet synliggörs de olika momenten som ingår i en laboration eller i en undersökning. Vilken är forskningsfrågan, hur planerar man att söka svar på sin fråga, vilka resultat har man kommit till och vilka slutsatser kan man dra? V-diagrammet innehåller också en teoretisk och begreppslig sida där laborationens teoretiska förankring synliggörs. Resultaten från undersökningen visar att arbetet med öppna laborationer i kombination med V-diagram hade positiv inverkan på elevernas uppfattning om sitt eget lärande. Eleverna upplevde att laborationerna krävde tänkande men att detta samtidigt ledde till förståelse. Eleverna hjälpte varandra att försöka förstå då de gemensamt skulle lösa problem. I diskussionen med sina kamrater och med läraren fick eleverna möjlighet att formulera sina egna uppfattningar och konfrontera dem mot andra uppfattningar. V-diagrammets struktur fungerade som vägledning då eleverna planerade sin laboration, men gav också en överblick över laborationer i efterhand då eleverna förberedde sig inför kursprovet, vilket för en del elever bidrog till deras förståelse. Grupperna var i allmänhet mycket fokuserade på uppgiften då de planerade en öppen laboration. Laborationerna hade alla en förankring i vardagen vilket gjorde att eleverna kunde göra kopplingar mellan sina egna erfarenheter och laborationen. Majoriteten av eleverna uppgav efter kemikursen att de upplevt den som intressant och laborationerna lyftes fram speciellt. De öppna laborationerna ställde stora krav på laborationsgrupperna och på elevernas samarbetsförmåga och gjorde laborationerna känsliga för grupprelaterade problem, genom att eleverna skulle klara av utmaningar gemensamt. För en elev med svag självuppfattning kan tillrättalagda laborationer med klara instruktioner kännas tryggare än en öppen laboration, där utmaningen är större. Samtidigt hade just utmaningarna, som var på en nivå som eleverna klarade av efter att ha tänkt och diskuterat med varandra, en positiv inverkan på självuppfattningen för ett flertal av eleverna. Att klara av utmaningar på rätt nivå kan inverka positivt på den egna själuppfattningen. De öppna laborationerna ställer krav på läraren att vara flexibel och kunna gå in i rollen av bl.a. handledare och coach. Samtidigt utgör lärare en representant för det naturvetenskapliga samfundet och har ansvar för att göra teori och begrepp tillgängliga för eleverna då de behöver dessa i sina undersökningar. För lärare kan de öppna laborationerna kännas problematiska, eftersom de själva sällan har erfarenheter av denna typ av laborationer från sin egen skoltid eller utbildning.

Otimização do layout de marcenarias no sul do espírito santo baseado em parâmetros ergonômicos e de produtividade

Este estudo foi realizado em três marcenarias no sul do Estado do Espírito Santo, com o objetivo de analisar o layout e propor mudanças que otimizem o funcionamento harmônico entre o local de trabalho e o trabalhador, considerando-se fatores ergonômicos, fluxo de produção e produtividade. A coleta de dados foi feita analisando-se as condições do ambiente de trabalho (clima, ruído, iluminação) e aplicando uma entrevista para avaliar as condições gerais e de segurança no trabalho. O layout foi avaliado por medições, observação da sequência de trabalho nas máquinas e aplicação do software AutoCAD 2000. Os resultados indicaram que o Índice de Bulbo Úmido e o Termômetro de Globo estavam de acordo com a Norma Regulamentadora nº 15 (atividade moderada), sendo de 26,38 ºC, em média. Os níveis médios de ruído foram de 87,48 dB (A), acima do permitido para uma jornada de 8 h diárias (NR 15). A luminosidade média, encontrada em duas marcenarias, ficou acima da faixa de iluminação mínima recomendada para esse trabalho de maquinarias (NBR 5413/92). Todas as marcenarias tinham disposição desordenada do maquinário em razão da sequência lógica de trabalho, presença de pilastras e resíduos na área útil e de passagem, piso desnivelado, falta de rampas para acesso aos galpões, manutenção de máquinas e equipamentos de forma incorreta, falhas no telhado e ausência de bancadas para facilitar a adoção de uma melhor postura durante o manuseio das peças.

Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

Application of Computational Fluid Dynamics in Modeling Blood Flow in Human Thoracic Aorta

The aim of this study was to simulate blood flow in thoracic human aorta and understand the role of flow dynamics in the initialization and localization of atherosclerotic plaque in human thoracic aorta. The blood flow dynamics in idealized and realistic models of human thoracic aorta were numerically simulated in three idealized and two realistic thoracic aorta models. The idealized models of thoracic aorta were reconstructed with measurements available from literature, and the realistic models of thoracic aorta were constructed by image processing Computed Tomographic (CT) images. The CT images were made available by South Karelia Central Hospital in Lappeenranta. The reconstruction of thoracic aorta consisted of operations, such as contrast adjustment, image segmentations, and 3D surface rendering. Additional design operations were performed to make the aorta model compatible for the numerical method based computer code. The image processing and design operations were performed with specialized medical image processing software. Pulsatile pressure and velocity boundary conditions were deployed as inlet boundary conditions. The blood flow was assumed homogeneous and incompressible. The blood was assumed to be a Newtonian fluid. The simulations with idealized models of thoracic aorta were carried out with Finite Element Method based computer code, while the simulations with realistic models of thoracic aorta were carried out with Finite Volume Method based computer code. Simulations were carried out for four cardiac cycles. The distribution of flow, pressure and Wall Shear Stress (WSS) observed during the fourth cardiac cycle were extensively analyzed. The aim of carrying out the simulations with idealized model was to get an estimate of flow dynamics in a realistic aorta model. The motive behind the choice of three aorta models with distinct features was to understand the dependence of flow dynamics on aorta anatomy. Highly disturbed and nonuniform distribution of velocity and WSS was observed in aortic arch, near brachiocephalic, left common artery, and left subclavian artery. On the other hand, the WSS profiles at the roots of branches show significant differences with geometry variation of aorta and branches. The comparison of instantaneous WSS profiles revealed that the model with straight branching arteries had relatively lower WSS compared to that in the aorta model with curved branches. In addition to this, significant differences were observed in the spatial and temporal profiles of WSS, flow, and pressure. The study with idealized model was extended to study blood flow in thoracic aorta under the effects of hypertension and hypotension. One of the idealized aorta models was modified along with the boundary conditions to mimic the thoracic aorta under the effects of hypertension and hypotension. The results of simulations with realistic models extracted from CT scans demonstrated more realistic flow dynamics than that in the idealized models. During systole, the velocity in ascending aorta was skewed towards the outer wall of aortic arch. The flow develops secondary flow patterns as it moves downstream towards aortic arch. Unlike idealized models, the distribution of flow was nonplanar and heavily guided by the artery anatomy. Flow cavitation was observed in the aorta model which was imaged giving longer branches. This could not be properly observed in the model with imaging containing a shorter length for aortic branches. The flow circulation was also observed in the inner wall of the aortic arch. However, during the diastole, the flow profiles were almost flat and regular due the acceleration of flow at the inlet. The flow profiles were weakly turbulent during the flow reversal. The complex flow patterns caused a non-uniform distribution of WSS. High WSS was distributed at the junction of branches and aortic arch. Low WSS was distributed at the proximal part of the junction, while intermedium WSS was distributed in the distal part of the junction. The pulsatile nature of the inflow caused oscillating WSS at the branch entry region and inner curvature of aortic arch. Based on the WSS distribution in the realistic model, one of the aorta models was altered to induce artificial atherosclerotic plaque at the branch entry region and inner curvature of aortic arch. Atherosclerotic plaque causing 50% blockage of lumen was introduced in brachiocephalic artery, common carotid artery, left subclavian artery, and aortic arch. The aim of this part of the study was first to study the effect of stenosis on flow and WSS distribution, understand the effect of shape of atherosclerotic plaque on flow and WSS distribution, and finally to investigate the effect of lumen blockage severity on flow and WSS distributions. The results revealed that the distribution of WSS is significantly affected by plaque with mere 50% stenosis. The asymmetric shape of stenosis causes higher WSS in branching arteries than in the cases with symmetric plaque. The flow dynamics within thoracic aorta models has been extensively studied and reported here. The effects of pressure and arterial anatomy on the flow dynamic were investigated. The distribution of complex flow and WSS is correlated with the localization of atherosclerosis. With the available results we can conclude that the thoracic aorta, with complex anatomy is the most vulnerable artery for the localization and development of atherosclerosis. The flow dynamics and arterial anatomy play a role in the localization of atherosclerosis. The patient specific image based models can be used to diagnose the locations in the aorta vulnerable to the development of arterial diseases such as atherosclerosis.