Discription of a New Calculation Method for Determination of Stoichiometric Dissociation Constants of WeakAcid in Salt Solutions from Potentiometric Titration Data

A recently developed calculation method to determine stoichiometric dissociation constants of weak acids from potentiometric titration data is described. The titration data from three different weak acids in aqueous salt solutions at 25 °C were used as examples of the use of the method. The salt alone determined the ionic strength of the solutions considered in this study, and salt molalities up to 0,5 mol kg -1 were used.

Potentiometric titration as a method of determining the stoichiometric dissociation constants of weak acids from the thermodynamic dissociation constants of aqueous solutions at 298.15 K

The simple single-ion activity coefficient equation originating from the Debye-Hückel theory was used to determine the thermodynamic and stoichiometric dissociation constants of weak acids from data concerning galvanic cells. Electromotive force data from galvanic cells without liquid junctions, which was obtained from literature, was studied in conjuction with the potentiometric titration data relating to aqueous solutions at 298.15 K. The dissociation constants of weak acids could be determined by the presented techniques and almost all the experimental data studied could be interpreted within the range of experimental error. Potentiometric titration has been used here and the calculation methods were developed to obtain the thermodynamic and stoichiometric dissociation constants of some weak acids in aqueous solutions at 298.15 K. The ionic strength of titrated solutions were adjusted using an inert electrolyte, namely, sodium or potassium chloride. Salt content alonedetermines the ionic strength. The ionic strength of the solutions studied varied from 0.059 mol kg-1 to 0.37 mol kg-1, and in some cases up to 1.0 mol kg-1. The following substances were investigated using potentiometric titration: aceticacid, propionic acid, L-aspartic acid, L-glutamic acid and bis(2,2-dimethyl-3-oxopropanol) amine.

Vasicek interest rate model

Tässä tutkielmassa estimoidaan korkomallin parametrit Maximum likelihood metodilla sekä näytetään kuinka mallintaa lyhyen koron evoluutiota ja korkokäyrän rakennetta.

Kromatografinen erotus bioetanolin valmistuksessa lignoselluloosasta

Bioetanolin tuotanto kiinnostaa monissa maissa johtuen kansainvälisissä sopimuksissa määritellyistä ilmastotavoitteista. Työssä tutkittiin laboratorio-oloissa ioninvaihtohartsien ominaisuuksien ja erotuksen olosuhteiden vaikutusta rikkihapon ja glukoosin kromatografiseen erotukseen. Tehokkaimmaksi hartsiksi osoittautui polysulfonoitu mesohuokoinen vahva kationinvaihtohartsi Finex CS100C. CS100C:lla voitiin erottaa rikkihappoa ja glukoosia tehokkaimmin korkeissa 25 p-% ja 36 p-% glukoosi- ja rikkihappo-pitoisuuksissa. Lisäksi sillä havaittiin suurin tuotto simuloidussa liikkuvassa pedissä. Yhdessä kolonnissa suoritetuissa erotuskokeissa tutkittiin hartsien erotuskykyä rikkihapolle ja glukoosille sekä virtausnopeuden vaikutusta erotukseen lämpötilassa 22 °C. Saatujen tulosten pohjalta valittiin CS11GC, CS16GC ja CS100C tarkempaan isotermin määritykseen ja simulointiin hyvän erotuskyvyn sekä keskinäisten erojen takia. Adsorptioisotermit määritettiin kolonnikokein sekä 22 °C:n että 50 °C:n lämpötilassa. Isotermeistä havaittiin, että tasapaino kiinto- ja liuosfaasien välille saavutetaan rikkihapolla alhaisella 1 cm3/min virtausnopeudella varmemmin kuin suuremmalla 2,5 cm3/min virtausnopeudella. 50 °C:n lämpötilassa hapon ja glukoosin isotermit olivat jyrkempiä kuin 22 °C:n lämpötilassa. Määritettyihin hapon ja sokerin isotermeihin sovitettiin mallit, joiden parametreja käytettiin yksittäisen kolonnin simulointiin. Simuloinnissa oli estimoitavia parametreja yhdellä kolonnilla aineensiirtokertoimet sekä läpäisykäyristä määritetyt isotermiparametrit glukoosille sekä rikkihapolle ja SMB–erotuksessa vyöhykkeiden 2 ja 3 suhteelliset virtausnopeudet. Siirryttäessä lämpötilojen 22 °C ja 50 °C välillä hartsien parametrit muuttuivat sokerille täysin ja hapolle vain aineensiirtokertoimen osalta. CS100C oli tehokkain SMB–erotuksessa korkeimmalla 0,11 cm3/min tuottavuudella 95 %:n saannon saavuttamiseksi 95 % tuotepuhtaudella raffinaatissa ja ekstraktissa.

Ecological and Epidemiological Analyses of Multiple Sclerosis Relapse Rate

The underlying cause of many human autoimmune diseases is unknown, but several environmental factors are implicated in triggering the self-destructive immune reactions. Multiple Sclerosis (MS) is a chronic autoimmune disease of the central nervous system, potentially leading to persistent neurological deterioration. The cause of MS is not known, and apart from immunomodulatory treatments there is no cure. In the early phase of the disease, relapsing-remitting MS (RR-MS) is characterized by unpredictable exacerbations of the neurological symptoms called relapses, which can occur at different intervals ranging from 4 weeks to several years. Microbial infections are known to be able to trigger MS relapses, and the patients are instructed to avoid all factors that might increase the risk of infections and to properly use antibiotics as well as to take care of dental hygiene. Among those environmental factors which are known to increase susceptibility to infections, high ambient air inhalable particulate matter levels affect all people within a geographical region. During the period of interest in this thesis, the occurrence of MS relapses could be effectively reduced by injections of interferon, which has immunomodulatory and antiviral properties. In this thesis, ecological and epidemiological analyses were used to study the possible connection between MS relapse occurrence, population level viral infections and air quality factors, as well as the effects of interferon medication. Hospital archive data were collected retrospectively from 1986-2001, a period in time ranging from when interferon medication first became available until just before other disease-modifying MS therapies arrived on the market. The grouped data were studied with logistic regression and intervention analysis, and individual patient data with survival analysis. Interferons proved to be effective in the treatment of MS in this observational study, as the amount of MS exacerbations was lower during interferon use as compared to the time before interferon treatment. A statistically significant temporal relationship between MS relapses and inhalable particular matter (PM₁₀) concentrations was found in this study, which implies that MS patients are affected by the exposure to PM₁₀. Interferon probably protected against the effect of PM₁₀, because a significant increase in the risk of exacerbations was only observed in MS patients without interferon medication following environmental exposure to population level specific viral infections and PM₁₀. Apart from being antiviral, interferon could thus also attenuate the enhancement of immune reactions caused by ambient air PM₁₀. The retrospective approach utilizing carefully constructed hospital records proved to be an economical and reliable source of MS disease information for statistical analyses.

The determination of EONIA rate: The impact of the financial crisis and the effects of the changes in the monetary policy implementation framework

EONIA is a market based overnight interest rate, whose role as the starting point of the yield curve makes it critical from the perspective of the implementation of European Central Bank´s common monetary policy in the euro area. The financial crisis that started in 2007 had a large impact on the determination mechanism of this interest rate, which is considered as the central bank´s operational target. This thesis examines the monetary policy implementation framework of the European Central Bank and changes made to it. Furthermore, we discuss the development of the recent turmoil in the money market. EONIA rate is modelled by means of a regression equation using variables related to liquidity conditions, refinancing need, auction results and calendar effects. Conditional volatility is captured by an EGARCH model, and autocorrelation is taken into account by employing an autoregressive structure. The results highlight how the tensions in the initial stage of the market turmoil were successfully countered by ECB´s liquidity policy. The subsequent response of EONIA to liquidity conditions under the full allotment liquidity provision procedure adopted after the demise of Lehman Brothers is also established. A clear distinction in the behavior of the interest rate between the sub-periods was evident. In the light of the results obtained, some of the challenges posed by the exit-strategy implementation will be addressed.

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.

Improving the calculation of rate of stratification in APROS

APROS (Advanced Process Simulation Environment) is a computer simulation program developed to simulate thermal hydraulic processes in nuclear and conventional power plants. Earlier research at VTT Technological Research Centre of Finland had found the current version of APROS to produce inaccurate simulation results for a certain case of loop seal clearing. The objective of this Master’s thesis is to find and implement an alternative method for calculating the rate of stratification in APROS, which was found to be the reason for the inaccuracies. Brief literature study was performed and a promising candidate for the new method was found. The new method was implemented into APROS and tested against experiments and simulations from two test facilities and the current version of APROS. Simulation results with the new version were partially conflicting; in some cases the new method was more accurate than the current version, in some the current method was better. Overall, the new method can be assessed as an improvement.

A study on rate correlations of gasification reactions

Gasification offers an environmentally friendly alternative for conventional combustion enabling the use of low grade and troublesome fuel such as municipal waste. While combustion converts fuel directly into thermal energy and noxious gases, gasification thermally converts fuel into gas that can be used in multiple applications. The purpose of this work is to get to know the gasification as a phenomenon and examine the kinetics of gasification. The main interest is in the reaction rates of the most important gasification reactions - water-gas, Boudouard and shift reaction. Reaction rate correlations found in the scientific articles are examined in atmospheric pressure in different temperatures.