TitGer: uma planilha eletrônica para simulação de titulação de mistura de compostos polipróticos

The aim of this paper is to present a simple way of treating the general equation for acid-base titrations based on the concept of degree of dissociation, and to propose a new spreadsheet approach for simulating the titration of mixtures of polyprotic compounds. The general expression, without any approximation, is calculated a simple iteration method, making number manipulation easy and painless. The user-friendly spreadsheet was developed by using MS-Excel and Visual-Basic-for-Excel. Several graphs are drawn for helping visualizing the titration behavior. A Monte Carlo function for error simulation was also implemented. Two examples for titration of alkalinity and McIlvaine buffer are presented.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.

Entorn de gestió de dades d'ornitologia

Des de fa uns anys, des de l’EPS de la UVic, s’està duent a terme el desenvolupament d’un dispositiu electrònic que proporciona la capacitat de capturar dades sobre un niu d’ocells. El projecte e-niu, que es pot seguir a www.tutara.info/e-niu, està actualment en una fase de test., i s’ha desenvolupat sobretot la part hardware. Aquest projecte té com a objectiu principal crear un entorn web per poder gestionar les dades que s’obtenen del niu d’ocells informatitzat (e-niu). Les dades que ens arriben dels e-nius estan en un arxiu de text, i el que es pretén és que l’usuari que controla el niu, pugui fer diversos anàlisis de les dades d’aquest. A més de poder veure els resultats en diversos tipus de gràfics, també se li vol donar la opció de treure els resultats en format taula o en format Excel, un format aquest últim, molt interessant, ja que donaria a les dades una gran possibilitat de ser tractades posteriorment, com fer seleccions del tipus de dades, treure percentatges, crear altres tipus de gràfics, etc. L’altre gran objectiu és el fet de poder treballar en la creació d’un entorn web complert a nivell gairebé professional amb l’aprenentatge que això comporta, ja que s’ha aplicat la tecnologia client-servidor, és a dir, que el llenguatge de programació està dins el servidor, i quan algun usuari l’executa, el sistema només li envia la presentació en HTML. El sistema de programació que es fa servir és el de les tres capes. La capa de dades, que està formada per una base de dades relacional del tipus MySQL i és on emmagatzemarem tota la informació. La capa de programació de la que s’encarrega el llenguatge PHP, és on s’efectua tot el tractament de les dades i finalment, la capa de presentació, que és la que s’encarrega de mostrar les dades al client en el navegador mitjançant els templates de HTML.

Combined application of continuous wavelet transform-zero crossing technique in the simultaneous spectrophotometric determination of perindopril and indapamid in tablets

Signal processing methods based on the combined use of the continuous wavelet transform (CWT) and zero-crossing technique were applied to the simultaneous spectrophotometric determination of perindopril (PER) and indapamide (IND) in tablets. These signal processing methods do not require any priory separation step. Initially, various wavelet families were tested to identify the optimum signal processing giving the best recovery results. From this procedure, the Haar and Biorthogonal1.5 continuous wavelet transform (HAAR-CWT and BIOR1.5-CWT, respectively) were found suitable for the analysis of the related compounds. After transformation of the absorbance vectors by using HAAR-CWT and BIOR1.5-CWT, the CWT-coefficients were drawn as a graph versus wavelength and then the HAAR-CWT and BIOR1.5-CWT spectra were obtained. Calibration graphs for PER and IND were obtained by measuring the CWT amplitudes at 231.1 and 291.0 nm in the HAAR-CWT spectra and at 228.5 and 246.8 nm in BIOR1.5-CWT spectra, respectively. In order to compare the performance of HAAR-CWT and BIOR1.5-CWT approaches, derivative spectrophotometric (DS) method and HPLC as comparison methods, were applied to the PER-IND samples. In this DS method, first derivative absorbance values at 221.6 for PER and 282.7 nm for IND were used to obtain the calibration graphs. The validation of the CWT and DS signal processing methods was carried out by using the recovery study and standard addition technique. In the following step, these methods were successfully applied to the commercial tablets containing PER and IND compounds and good accuracy and precision were reported for the experimental results obtained by all proposed signal processing methods.

Evaluation of pesticide adsorption in gas chromatographic injector and column

Components in complex matrices can cause variations in chromatographic response during analysis of pesticides by gas chromatography. These variations are related to the competition between analytes and matrix components for adsorption sites in the chromatographic system. The capacity of the pesticides chlorpyrifos and deltamethrin to be adsorbed in the injector and chromatographic column was evaluated by constructing three isotherms and changing the column heating rate to 10 and 30 ºC min-1. By using ANCOVA to compare the slope of calibration graphs, results showed that the higher the injector temperature (310 ºC) the lower the pesticide adsorption. Also, deltamethrin influenced the adsorption of chlorpyrifos on the column chromatographic.

Software para simulação de mecanismo de supressão da luminescência: modelo cinético de Stern-Volmer

A software that includes both Stochastic and Molecular Dynamics procedures has been developed with the aim of visualizing the Stern-Volmer kinetic mechanism of dynamic luminescence quenching. The software allows the student to easily simulate and graphically visualize the molecular collisions, the molecular speed distributions, the luminescence decay curves, and the Stern-Volmer graphs. The software named "SternVolmer" is written for the FreeBASIC compiler and can be applied to dynamic systems where luminescent molecules, during their excited state lifetimes, are able to collide with quenching molecules (collisional quenching). The good agreement found between the simulations and the expected results shows that this software can be used as an effective teaching aid for the study of luminescence and kinetic decay of excited states.

Methods and Models for Accelerating Dynamic Simulation of Fluid Power Circuits

The objective of this dissertation is to improve the dynamic simulation of fluid power circuits. A fluid power circuit is a typical way to implement power transmission in mobile working machines, e.g. cranes, excavators etc. Dynamic simulation is an essential tool in developing controllability and energy-efficient solutions for mobile machines. Efficient dynamic simulation is the basic requirement for the real-time simulation. In the real-time simulation of fluid power circuits there exist numerical problems due to the software and methods used for modelling and integration. A simulation model of a fluid power circuit is typically created using differential and algebraic equations. Efficient numerical methods are required since differential equations must be solved in real time. Unfortunately, simulation software packages offer only a limited selection of numerical solvers. Numerical problems cause noise to the results, which in many cases leads the simulation run to fail. Mathematically the fluid power circuit models are stiff systems of ordinary differential equations. Numerical solution of the stiff systems can be improved by two alternative approaches. The first is to develop numerical solvers suitable for solving stiff systems. The second is to decrease the model stiffness itself by introducing models and algorithms that either decrease the highest eigenvalues or neglect them by introducing steady-state solutions of the stiff parts of the models. The thesis proposes novel methods using the latter approach. The study aims to develop practical methods usable in dynamic simulation of fluid power circuits using explicit fixed-step integration algorithms. In this thesis, twomechanisms whichmake the systemstiff are studied. These are the pressure drop approaching zero in the turbulent orifice model and the volume approaching zero in the equation of pressure build-up. These are the critical areas to which alternative methods for modelling and numerical simulation are proposed. Generally, in hydraulic power transmission systems the orifice flow is clearly in the turbulent area. The flow becomes laminar as the pressure drop over the orifice approaches zero only in rare situations. These are e.g. when a valve is closed, or an actuator is driven against an end stopper, or external force makes actuator to switch its direction during operation. This means that in terms of accuracy, the description of laminar flow is not necessary. But, unfortunately, when a purely turbulent description of the orifice is used, numerical problems occur when the pressure drop comes close to zero since the first derivative of flow with respect to the pressure drop approaches infinity when the pressure drop approaches zero. Furthermore, the second derivative becomes discontinuous, which causes numerical noise and an infinitely small integration step when a variable step integrator is used. A numerically efficient model for the orifice flow is proposed using a cubic spline function to describe the flow in the laminar and transition areas. Parameters for the cubic spline function are selected such that its first derivative is equal to the first derivative of the pure turbulent orifice flow model in the boundary condition. In the dynamic simulation of fluid power circuits, a tradeoff exists between accuracy and calculation speed. This investigation is made for the two-regime flow orifice model. Especially inside of many types of valves, as well as between them, there exist very small volumes. The integration of pressures in small fluid volumes causes numerical problems in fluid power circuit simulation. Particularly in realtime simulation, these numerical problems are a great weakness. The system stiffness approaches infinity as the fluid volume approaches zero. If fixed step explicit algorithms for solving ordinary differential equations (ODE) are used, the system stability would easily be lost when integrating pressures in small volumes. To solve the problem caused by small fluid volumes, a pseudo-dynamic solver is proposed. Instead of integration of the pressure in a small volume, the pressure is solved as a steady-state pressure created in a separate cascade loop by numerical integration. The hydraulic capacitance V/Be of the parts of the circuit whose pressures are solved by the pseudo-dynamic method should be orders of magnitude smaller than that of those partswhose pressures are integrated. The key advantage of this novel method is that the numerical problems caused by the small volumes are completely avoided. Also, the method is freely applicable regardless of the integration routine applied. The superiority of both above-mentioned methods is that they are suited for use together with the semi-empirical modelling method which necessarily does not require any geometrical data of the valves and actuators to be modelled. In this modelling method, most of the needed component information can be taken from the manufacturer’s nominal graphs. This thesis introduces the methods and shows several numerical examples to demonstrate how the proposed methods improve the dynamic simulation of various hydraulic circuits.

Evaluating multidimensional visualization techniques in data mining tasks

Visual data mining (VDM) tools employ information visualization techniques in order to represent large amounts of high-dimensional data graphically and to involve the user in exploring data at different levels of detail. The users are looking for outliers, patterns and models – in the form of clusters, classes, trends, and relationships – in different categories of data, i.e., financial, business information, etc. The focus of this thesis is the evaluation of multidimensional visualization techniques, especially from the business user’s perspective. We address three research problems. The first problem is the evaluation of projection-based visualizations with respect to their effectiveness in preserving the original distances between data points and the clustering structure of the data. In this respect, we propose the use of existing clustering validity measures. We illustrate their usefulness in evaluating five visualization techniques: Principal Components Analysis (PCA), Sammon’s Mapping, Self-Organizing Map (SOM), Radial Coordinate Visualization and Star Coordinates. The second problem is concerned with evaluating different visualization techniques as to their effectiveness in visual data mining of business data. For this purpose, we propose an inquiry evaluation technique and conduct the evaluation of nine visualization techniques. The visualizations under evaluation are Multiple Line Graphs, Permutation Matrix, Survey Plot, Scatter Plot Matrix, Parallel Coordinates, Treemap, PCA, Sammon’s Mapping and the SOM. The third problem is the evaluation of quality of use of VDM tools. We provide a conceptual framework for evaluating the quality of use of VDM tools and apply it to the evaluation of the SOM. In the evaluation, we use an inquiry technique for which we developed a questionnaire based on the proposed framework. The contributions of the thesis consist of three new evaluation techniques and the results obtained by applying these evaluation techniques. The thesis provides a systematic approach to evaluation of various visualization techniques. In this respect, first, we performed and described the evaluations in a systematic way, highlighting the evaluation activities, and their inputs and outputs. Secondly, we integrated the evaluation studies in the broad framework of usability evaluation. The results of the evaluations are intended to help developers and researchers of visualization systems to select appropriate visualization techniques in specific situations. The results of the evaluations also contribute to the understanding of the strengths and limitations of the visualization techniques evaluated and further to the improvement of these techniques.

AGRICULTURAL MACHINERY AND IMPLEMENTS DESIGN PROCESS: GUIDELINES FOR SMALL AND MID-SIZED BUSINESSES

ABSTRACT This study aims at presenting the process of machine design and agricultural implements by means of a reference model, formulated with the purpose of explaining the development activities of new products, serving as a guideline to coach human resources and to assist in formalizing the process in small and medium-sized businesses (SMB), i.e. up to 500 employees. The methodology used included the process modeling, carried out from case studies in the SMB, and the study of reference models in literature. The modeling formalism used was based on the IDEF0 standard, which identifies the dimensions required for the model detailing: input information; activities; tasks; knowledge domains; mechanisms; controls and information produced. These dimensions were organized in spreadsheets and graphs. As a result, a reference model with 27 activities and 71 tasks was obtained, distributed over four phases of the design process. The evaluation of the model was carried out by the companies participating in the case studies and by experts, who concluded that the model explains the actions needed to develop new products in SMB.

Tavoitevarastoarvojen määrittäminen uusille tuotteille - case: päivittäistavarakaupan yritys

Tämän tutkielman tarkoituksena oli löytää keinoja uusien tuotteiden tavoitevarastoarvojen määrittämisen helpottamiseksi case-yrityksessä. Ongelma on seurausta siitä, ettei uusille tuotteille ole saatavissa kysyntädataa. Oikeelliset tavoitevarastoarvot on tärkeitä case-yritykselle hävikin minimoimisen ja erityisesti asiakastyytyväisyyden vuoksi. Tutkittavaa aihetta lähestyttiin päivittäistavarakaupan strategisten menestystekijöiden sekä varastonhallinnan kautta. Teoriaosuuden pohjalta toteutettiin empiirinen osio, jossa etsittiin case-yrityksen kahden tuoteryhmän kysyntää selittäviä tekijöitä paneeliregression avulla. Ensin kuitenkin tutkittiin tuoteryhmien yleistä kysynnän rakennetta erilaisten kysyntäkuvaajien sekä korrelaatiomatriisien avulla. Tavoitevarastoarvoon eniten vaikuttava tekijä on kysyntä. Brändi ja hinta muodostuivat puolestaan vahvimmiksi kysyntää määrittäviksi muuttujiksi. Kysyntää arvioitaessa muut sitä nostavat muuttujat tulee aina miettiä tapauskohtaisesti. Mehukeitoilla kysyntää nostivat eniten vahva brändi ja suuri pakkauskoko. Juustoraasteilla puolestaan alhainen hinta ja pieni pakkauskoko olivat keskeisimmät myyntiin vaikuttavat tekijät. Tuoteryhmien muut kysyntää nostavat ominaisuudet olivat samoja, kuin tuoteryhmän suosituimmilla tuotteilla.

Höyryturbiinin käytönaikaisen suorituskyvyn seuranta

Tässä diplomityössä jatkettiin Loviisan voimalaitoksen höyryturbiinien suorituskyvyn parannuspotentiaalien tutkimusta. Tavoitteena oli kehittää laitoksen höyryturbiinien suorituskyvyn käytönaikaisia on-line-mittauksia. Selvityksessä perehdyttiin norjalaisen IFE:n kehittämään stationääritilan TEMPOohjelmaan( The Thermal Performance Monitoring And Optimisation system), sen käyttöohjeisiin ja toimintaperiaatteisiin. Työssä esiteltiin laajasti tiedon yhteensovittamisen laskentateoriaa, johon TEMPOn toiminta perustuu. Työssä tarkasteltiin turbiinin todellista paisuntaprosessia, koska sen ymmärtäminen on tärkeässä osassa turbiinin suorituskyvyn valvonnassa. Tutkimuksessa esiteltiin myös turbiineille mahdollisia vikoja sekä niiden syntymisprosesseja. Työssä tarkasteltiin TEMPOn sovittamien tulostiedostojen analysointiohjelman toimivuutta havaitsemalla itse aiheutettuja poikkeamia todellisiin mittaustiedostoihin. Analysointiohjelmalla muodostettuja kuvaajia vertailtiin todellisen prosessin ajotilanteen kuvaajiin ja tarkasteltiin, kuinka poikkeamia on mahdollista havaita kuvaajien avulla. TEMPO-ohjelmalle löydettiin tutkimuksen edetessä kehittämisehdotuksia. Näillä muutoksilla ohjelma saadaan mallintamaan Loviisan voimalaitoksen turbiiniprosessia tarkemmin ja tuloksista saadaan hyödyllisempiä.

Talviaikainen happitilanne eräissä Pohjois-Savon järvissä vuosina 1997-2008

Pohjois-Savossa seurattiin talviaikaista happitilannetta vuosina 1997-2008. Seurannan kohteena oli neljä pienehköä järveä (Iso-Valkeinen, Kevätön, Kolmisoppi ja Vehmasjärvi), jotka ovat erityyppisiä syvyydeltään, rehevyystasoltaan ja humuspitoisuudeltaan. Näiden esimerkkijärvien oli tarkoitus antaa yleisemminkin viitteitä happitilanteen kehityksestä talven aikana. Alkutalven tulosten perusteella annettiin vuosittain tiedote, jossa arvioitiin happikatojen mahdollisuutta kevättalven kuluessa. Yleisöllä oli myös mahdollisuus seurata happi- ja lämpötilatuloksia Pohjois-Savon ympäristökeskuksen verkkopalvelun kautta. Hapenkulutusnopeus oli rehevimmässä seurantajärvessä kaksinkertainen verrattuna karumpiin ja syvyyden myötä ero vain korostui. Pohjanläheisessä vesikerroksessa 1 mg/l:n happipitoisuus kului karuissa järvissä noin kahdessa viikossa ja rehevässä noin kolmessa päivässä. Vuosien välinen vaihtelu oli kuitenkin hyvin suurta. Vaihtelu oli suurta myös karuissa järvissä. Veden jäätymisajankohdalla ja veden lämpötilalla on merkittävä vaikutus siihen, millainen kevättalven happitilanteesta muodostui. Seurantajärvien aineiston perusteella voidaan karkeasti arvioida, että kuukauden viivästyminen jäätymisessä tai vesipatsaan viilentyminen ennen jäätymistä asteen verran kylmemmäksi merkitsevät noin kolmanneksen korkeampaa happipitoisuutta kevättalvella. Vesipatsaan happitilanteen heikentymisen sekä ravinne- ja rautapitoisuuksien välillä todettiin vahvat yhteydet. Kaikkien järvien aineistossa happitilanteen heikkeneminen johti voimakkaimmin alusveden ammoniumtyppi-, kokonaisfosfori- ja rautapitoisuuksien kasvuun. Pitoisuusmuutokset olivat talven aikana suurimmat rehevimmässä kohdejärvessä, Kevättömässä, jossa kokonaisfosforipitoisuudet keskimäärin kymmenkertaistuivat, fosfaattifosforipitoisuudet kasvoivat keskimäärin 20-kertaisiksi ja rautapitoisuudet yli seitsenkertaisiksi.

Phytosociological surveys: tools for weed science?

In simple terms, a phytosociological survey is a group of ecological evaluation methods whose aim is to provide a comprehensive overview of both the composition and distribution of plant species in a given plant community. To understand the applicability of phytosociological surveys for weed science, as well as their validity, their ecological basis should be understood and the most suitable ones need to be chosen, because cultivated fields present a relatively distinct group of selecting factors when compared to natural plant communities. For weed science, the following sequence of steps is proposed as the most suitable: (1) overall infestation; (2) phytosociological tables/graphs; (3) intra-characterization by diversity; (4) inter-characterization and grouping by cluster analysis. A summary of methods is established in order to assist Weed Science researchers through their steps into the realm of phytosociology.

CO2:n adsorptio Loviisan voimalaitoksen päästöilmasta 14C-päästöjen määrittämiseksi

Tämän kandidaatintyön tavoitteena oli selvittää mahdollisuuksia 14C:n kemiallisten muotojen eriyttämiseen käyttäen Loviisan voimalaitoksella olemassa olevaa näytteenkeräyslaitteistoa. Lisäksi tarkoituksena oli selvittää parhaiten tähän käyttötarkoitukseen soveltuva zeoliittityyppiä tyypeistä 4A, 5A ja 13X. Työn kirjallisessa osassa käsitellään ydinvoimalaitoksen C14-päästöjä keskittyen pääosin Loviisan VVER-laitokseen. Adsorption osalta esitellään kaupallisesti käytettyjä adsorptiomateriaaleja ja paneudutaan adsorptioon fysikaalisena ja kemiallisena ilmiönä. Lisäksi esitellään kahden desorptiomenetelmän perusperiaatteet. Kirjallisen osan lopussa kootaan tutkimukseen vaikuttavia tekijöitä ja esitellään aiemmin käytössä ollut näytteenkeräyslaitteisto. Kokeellisessa osassa esitellään työssä käytetyt laitteistot. Lisäksi on kuvattu mittausten suoritus nestetuikelaskurilla. Tämän jälkeen työssä esitellään mittaustuloksien käsittely ja näin saadut tulokset.

Energy saving potential in reservoir pumping

Pumping systems account for up to 22 % of the energy consumed by electrical motors in European industry. Many studies have shown that there is also a lot of potential for energy savings in these systems with the improvement of devices, flow control or surrounding sys-tem. The best method for more energy efficient pumping has to be found for each system separately. This thesis studies how energy saving potential in reservoir pumping system is affected by surrounding variables, such as the static head variation and friction factor. The objective is to create generally applicable graphs to quickly compare methods for reducing pumping system’s energy costs. The gained results are several graphs showcasing how the chosen variables affect energy saving potential of the pumping system in one specific case. To judge if these graphs are generally applicable, more testing with different pumps and environments are required.