Stabilization of the ionic form of weak acid cation exchange resins

Weak acid cation exchange (WAC) resins are used in the chromatographic separation of betaine from vinasse, a by-product of sugar industry. The ionic form of the resin determines the elution time of betaine. When a WAC-resin is in hydrogen form, the retention time of betaine is the longest and betaine elutes as the last component of vi-nasse from the chromatographic column. If the feed solution contains salts and its pH is not acidic enough to keep the resin undissociated, the ionic form of the hydrogen form resin starts to alter. Vinasse contains salts and its pH is around 5, it also contains weak acids. To keep the metal ion content (Na/H ratio) of the resin low enough to ensure successful separation of betaine, acid has to be added to either eluent (water) or vinasse. The aim of the present work was to examine by laboratory experiments which option requires less acid. Also the retention mechanism of betaine was investigated by measuring retention volumes of acetic acid and choline in different Na/H ratios of the resin. It was found that the resulting ionic form of the resin is the same regardless of whether the regeneration acid is added to the eluent or the feed solution (vinasse). Be-sides the salt concentration and the pH of vinasse, also the concentration of weak acids in the feed affects the resulting ionic form of the resin. The more buffering capacity vinasse has, the more acid is required to keep the ionic form of the resin desired. Vinasse was found to be quite strong buffer solution, which means relatively high amounts of acid are required to prevent the Na/H ratio from increasing too much. It is known that the retention volume of betaine decreases significantly, when the Na/H ratio increases. This is assumed to occur, because the amount of hydrogen bonds between the carboxylic groups of betaine and the resin decreases. Same behavior was not found with acetic acid. Choline has the same molecular structure as betaine, but instead of carboxylic group it has hydroxide group. The retention volume of choline increased as the Na/H ratio of the resin increased, because of the ion exchange reaction between choline cation and dissociated carboxylic group of the resin. Since the retention behavior of choline on the resin is opposite to the behavior of be-taine, the strong affinity of betaine towards hydrogen form WAC-resin has to be based on its carboxylic group. It is probable that the quaternary ammonium groups also affect the behavior of the carboxylic groups of betaine, causing them to form hydrogen bonds with the carboxylic groups of the resin.

Particle detector link system modifications in RE1/1 sector

The large hadron collider constructed at the European organization for nuclear research, CERN, is the world’s largest single measuring instrument ever built, and also currently the most powerful particle accelerator that exists. The large hadron collider includes six different experiment stations, one of which is called the compact muon solenoid, or the CMS. The main purpose of the CMS is to track and study residue particles from proton-proton collisions. The primary detectors utilized in the CMS are resistive plate chambers (RPCs). To obtain data from these detectors, a link system has been designed. The main idea of the link system is to receive data from the detector front-end electronics in parallel form, and to transmit it onwards in serial form, via an optical fiber. The system is mostly ready and in place. However, a problem has occurred with innermost RPC detectors, located in sector labeled RE1/1; transmission lines for parallel data suffer from signal integrity issues over long distances. As a solution to this, a new version of the link system has been devised, a one that fits in smaller space and can be located within the CMS, closer to the detectors. This RE1/1 link system has been so far completed only partially, with just the mechanical design and casing being done. In this thesis, link system electronics for RE1/1 sector has been designed, by modifying the existing link system concept to better meet the requirements of the RE1/1 sector. In addition to completion of the prototype of the RE1/1 link system electronics, some testing for the system has also been done, to ensure functionality of the design.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

Calculation of the variance in surveys of the economic climate

Public opinion surveys have become progressively incorporated into systems of official statistics. Surveys of the economic climate are usually qualitative because they collect opinions of businesspeople and/or experts about the long-term indicators described by a number of variables. In such cases the responses are expressed in ordinal numbers, that is, the respondents verbally report, for example, whether during a given trimester the sales or the new orders have increased, decreased or remained the same as in the previous trimester. These data allow to calculate the percent of respondents in the total population (results are extrapolated), who select every one of the three options. Data are often presented in the form of an index calculated as the difference between the percent of those who claim that a given variable has improved in value and of those who claim that it has deteriorated.

Utilisation of biomass for energy production in the North-West Russian forest industry

Traditionally, fossil fuels have always been the major sources of the modern energy production. However prices on these energy sources have been constantly increasing. The utilization of local biomass resources for energy production can substitute significant part of the required energy demand in different energy sectors. The introduction of the biomass usage can easily be started in the forest industry first as it possesses biomass in a large volume. The forest industry energy sector has the highest potential for the fast bioenergy development in the North-West Russia. Therefore, the question concerning rational and effective forest resources use is important today as well as the utilization of the forestry by-products. This work describes and analyzes the opportunities of utilising biomass, mainly, in the form of the wood by-products, for energy production processes in general, as well as for the northwest Russian forest industry conditions. The study also covers basic forest industry processes and technologies, so, the reader can get familiar with the information about the specific character of the biomass utilization. The work gives a comprehensive view on the northwest forest industry situation from the biomass utilisation point of view. By presenting existing large-scale sawmills and pulp and paper mills the work provides information for the evaluation of the future development of CHP investments in the northwest Russian forest industry.

Drag force and frictional resistances in vertically vibrated dense granular media

The objective of this thesis is to shed light on the vertical vibration of granular materials for potential interest in the power generation industry. The main focus is investigating the drag force and frictional resistance that influence the movement of a granular material (in the form of glass beads) contained in a vessel, which is subjected to sinusoidal oscillation. The thesis is divided into three parts: theoretical analysis, experiments and computer simulations. The theoretical part of this study presents the underlying physical phenomena of the vibration of granular materials. Experiments are designed to determine fundamental parameters that contribute to the behavior of vibrating granular media. Numerical simulations include the use of three different software applications: FLUENT, LS-DYNA and ANSYS Workbench. The goal of these simulations is to test theoretical and semiempirical models for granular materials in order to validate their compatibility with the experimental findings, to assist in predicting their behavior, and to estimate quantities that are hard to measure in laboratory.

Role of references in international industrial marketing : a theory-building case study about supplier’s processes of utilizing references

Scientific studies regarding specifically references do not seem to exist. However, the utilization of references is an important practice for many companies involved in industrial marketing. The purpose of the study is to increase the understanding about the utilization of references in international industrial marketing in order to contribute to the development of a theory of reference behavior. Specifically, the modes of reference usage in industry, the factors affecting a supplier's reference behavior, and the question how references are actually utilized, are explored in the study. Due to the explorative nature of the study, a research design was followed where theory and empirical studies alternated. An Exploratory Framework was developed to guide a pilot case study that resulted in Framework 1. Results of the pilot study guided an expanded literature review that was used to develop first a Structural Framework and a Process Framework which were combined in Framework 2. Then, the second empirical phase of the case study was conducted in the same (pilot) case company. In this phase, Decision Systems Analysis (DSA) was used as the analysis method. The DSA procedure consists of three interviewing waves: initial interviews, reinterviews, and validating interviews. Four reference decision processes were identified, described and analyzed in the form of flowchart descriptions. The flowchart descriptions were used to explore new constructs and to develop new propositions to develop Framework 2 further. The quality of the study was ascertained by many actions in both empirical parts of the study. The construct validity of the study was ascertained by using multiple sources of evidence and by asking the key informant to review the pilot case report. The DSA method itself includes procedures assuring validity. Because of the choice to conduct a single case study, external validity was not even pursued. High reliability was pursued through detailed documentation and thorough reporting of evidence. It was concluded that the core of the concept of reference is a customer relationship regardless of the concrete forms a reference might take in its utilization. Depending on various contingencies, references might have various tasks inside the four roles of increasing 1) efficiency of sales and sales management, 2) efficiency of the business, 3) effectiveness of marketing activities, and 4) effectiveness in establishing, maintaining and enhancing customer relationships. Thus, references have not only external but internal tasks as well. A supplier's reference behavior might be affected by many hierarchical conditions. Additionally, the empirical study showed that the supplier can utilize its references as a continuous, all pervasive decision making process through various practices. The process includes both individual and unstructured decision making subprocesses. The proposed concept of reference can be used to guide a reference policy recommendable for companies for which the utilization of references is important. The significance of the study is threefold: proposing the concept of reference, developing a framework of a supplier's reference behavior and its short term process of utilizing references, and conceptual structuring of an unstructured and in industrial marketing important phenomenon to four roles.

Model for interevent times with long tails and multifractality in human communications: An application to financial trading

Social, technological, and economic time series are divided by events which are usually assumed to be random, albeit with some hierarchical structure. It is well known that the interevent statistics observed in these contexts differs from the Poissonian profile by being long-tailed distributed with resting and active periods interwoven. Understanding mechanisms generating consistent statistics has therefore become a central issue. The approach we present is taken from the continuous-time random-walk formalism and represents an analytical alternative to models of nontrivial priority that have been recently proposed. Our analysis also goes one step further by looking at the multifractal structure of the interevent times of human decisions. We here analyze the intertransaction time intervals of several financial markets. We observe that empirical data describe a subtle multifractal behavior. Our model explains this structure by taking the pausing-time density in the form of a superstatistics where the integral kernel quantifies the heterogeneous nature of the executed tasks. A stretched exponential kernel provides a multifractal profile valid for a certain limited range. A suggested heuristic analytical profile is capable of covering a broader region.

Size distribution of atmospheric particulate ionic species at a coastal site in Portugal

A Berner impactor was used to collect size-differentiated aerosol samples from March to August 2003 in the city of Aveiro, on the Portuguese west coast. The samples were analysed for the main water-soluble ion species. The average concentration of sulphate, nitrate, chloride and ammonium was 6.38, 3.09, 1.67 and 1.27 µg m-3, respectively. The results show that SO4(2-) and NH4+ were consistently present in the fine fraction < 1 µm, which represents, on average, 72 and 89% of their total atmospheric concentrations, respectively. The NO3-particles were concentrated in the coarse size. Chloride presented the characteristic coarse mode for marine aerosols. During some spring/summer events, an ammonium surplus was observed (NH4+/SO4(2-) molar ratios > 2), possibly due to greater availability of ammonia coming from agricultural activities or from the neighbouring chemical industrial complex. During the remaining periods, the aerosol was found to be somewhat acidic and predominantly in the form of ammonium bisulphate (NH4+/SO4(2-) molar ratios = 0.5-1.25). Samples collected under a major or exclusive influence of maritime air masses were essentially constituted by coarse particles with enrichment in sea salt, while for air masses of continental origin the contribution of water-soluble ionic species in the fine mode was more pronounced.

Chelating Adsorbents in Purification of Hydrometallurgical Solutions

In this thesis, equilibrium and dynamic sorption properties of weakly basic chelating adsorbents were studied to explain removal of copper, nickel from a concentrated zinc sulfate solution in a hydrometallurgical process. Silica-supported chelating composites containing either branched poly(ethyleneimine) (BPEI) or 2-(aminomethyl)pyridine (AMP) as a functional group were used. The adsorbents are commercially available from Purity Systems Inc, USA as WP-1® and CuWRAM®, respectively. The fundamental interactions between the adsorbents, sulfuric acid and metal sulfates were studied in detail and the results were used to find the best conditions for removal of copper and nickel from an authentic ZnSO4 process solution. In particular, the effect of acid concentration and temperature on the separation efficiency was considered. Both experimental and modeling aspectswere covered in all cases. Metal sorption is considerably affected by the chemical properties of the studied adsorbents and by the separation conditions. In the case of WP-1, acid affinity is so high that column separation of copper, nickel and zinc has to be done using the adsorbent in base-form. On the other hand, the basicity of CuWRAM is significantly lower and protonated adsorbent can be used. Increasing temperature decreases the basicity and the metals affinity of both adsorbents, but the uptake capacities remain practically unchanged. Moreover, increasing temperature substantially enhances intra-particle mass transport and decreases viscosities thus allowing significantly higher feed flow rates in the fixed-bed separation. The copper selectivity of both adsorbents is very high even in the presence of a 250-fold excess of zinc. However, because of the basicity of WP-1, metal precipitation is a serious problem and therefore only CuWRAM is suitable for the practical industrial application. The optimum temperature for copper removal appears to be around 60 oC and an alternative solution purification method is proposed. The Ni/Zn selectivity of both WP-1 and CuWRAM is insufficient for removal of the very small amounts of nickel present in the concentrated ZnSO4 solution.

Counselling on limited preoperative fasting in paediatric ambulatory tonsillectomy

Rajoitetun preoperatiivisen paaston ohjaus lasten päiväkirurgisessa nielurisaleikkauksessa Tutkimuksen tarkoituksena oli selvittää, onko sairaanhoitajan toteuttama, vanhempien interaktiivinen preoperatiivinen ohjaus lapsen rajoitettuun preoperatiiviseen paastoon ja aktiiviseen nesteyttämiseen turvallista, kuinka vanhemmat omaksuvat kyseistä tietoa ja edistääkö se turvallisesti lapsen postoperatiivista toipumista päiväkirurgisen nielurisaleikkauksen jälkeen. Aineisto koostui sadastakuudestatoista perheestä, joiden lapsi, iältään 4 – 10 vuotta, oli kutsuttu päiväkirurgiseen nielurisaleikkaukseen. Koeryhmä (n= 58) ohjattiin interaktiivisesti lapsen preoperatiiviseen paastoon ja aktiiviseen preoperatiiviseen nesteyttämiseen. Lapsen suositellut preoperatiiviset paastoajat olivat: 4t syömättä ja 2t juomatta. Leikkauspäivän aamuna vanhemmat rohkaisivat lapsia juomaan annokset kirkkaita nesteitä kahteen otteeseen; jälkimmäinen annos 2t ennen leikkausta. Kontrolliryhmä (n= 58) sai preoperatiivisen ohjauksen kirjallisena ilman interaktiivista ohjausta; paastoajat olivat samat kuin koeryhmässä: 4t syömättä ja 2t juomatta. Vanhempien tiedontasoa lapsen leikkaukseen liittyvästä paastosta mitattiin tietotestillä, joka sisälsi myös preoperatiivista tiedontarvetta ja ahdistusta mittaavan mittarin (The Amsterdam Preoperative Anxiety and Information scale, APAIS). Mittaukset suoritettiin ennen preoperatiivista ohjausta tai kirjallisten ohjeiden lähettämistä sekä lapsen leikkausta seuraavana päivänä. Lapsen leikkauksen jälkeen vanhemmat arvioivat myös heille välitetyn informaation tasoa. Lapsen postoperatiivista kipua, pahoinvointia, janoa ja nälkää lapset itse arvioivat VAS- asteikolla (10cm), ja vanhemmat ja sairaanhoitajat numeerisella 0 – 10 asteikolla. Mittaukset suoritettiin 2t, 4t, 8t, ja 24t lapsen leikkauksen jälkeen. Vanhemmat pitivät päiväkirjaa lapsen ravinnosta ja kipulääkityksestä. Aineisto analysoitiin sekä tilastollisesti että sisällön analyysilla. Vanhempien tiedontaso lapsen leikkauksen jälkeen oli molemmissa ryhmissä merkitsevästi parantunut, mutta kontrolliryhmän vanhempien ahdistus ei ollut helpottanut verrattuna heidän ahdistukseensa ennen lapsen leikkausta. Mitä korkeammat pisteet vanhemmat saivat tietotestistä lapsen leikkauksen jälkeen sitä vähemmän he tunsivat tiedontarvetta ja ahdistusta. Merkitsevästi alhaisemmat pisteet tietotestistä oli vanhemmilla, joilla oli alempi peruskoulutus. Kontrolliryhmän lapset paastosivat preoperatiivisesti merkitsevästi pitempään kuin koeryhmän lapset. Perioperatiivisesti lapset paastosivat kiinteästä ruuasta yhtä kauan, mutta nesteistä kontrolliryhmä merkitsevästi pitempään. Postoperatiivisen toipumisen alussa koeryhmän lapset olivat merkitsevästi kivuttomampia. Molemmissa ryhmissä lapset olivat kipeimpiä kahdeksan tuntia leikkauksesta ja pahoinvointisimpia neljä tuntia leikkauksesta. Ensimmäisen kahdeksan tunnin aikana leikkauksen jälkeen lapset eivät olleet janoisia tai nälkäisiä, mutta VAS- arvot koeryhmässä jäivät alhaisemmalle tasolle kuin kontrolliryhmässä 24 postoperatiivisen tunnin ajan. Leikkausta seuraavana aamuna kontrolliryhmän lapset olivat merkitsevästi janoisempia ja nälkäisempiä kuin interventioryhmän lapset. Sairaanhoitajan toteuttama vanhempien interaktiivinen preoperatiivinen ohjaus lapsen rajoitettuun preoperatiiviseen paastoon lisää vanhempien tiedontasoa ja vähentää preoperatiivista tiedontarvettaan ja ahdistusta, ja turvallisesti parantaa lapsen kokemusta leikkausprosessin ja postoperatiivisen toipumisen aikana nielurisaleikkauksen jälkeen. Kaikkien leikkaukseen tulevien lasten nesteyttäminen kaksi tuntia ennen päivän ensimmäistä leikkausta voi olla ratkaisu lasten kohtuuttomien perioperatiivisten paastoaikojen estämiseksi. Aina ei kuitenkaan ole mahdollisuuksia vanhempien henkilökohtaiseen kohtaamiseen, mikä haastaa hoitotieteellisen tutkimuksen kartoittamaan muita mahdollisuuksia vanhempien interaktiiviseen ohjaukseen.

Caracterização de membranas assimétricas de acetato de celulose produzidas a partir do aproveitamento do resíduo da palha de milho para uso em ultrafiltração

Cellulose acetates (CA) with different degrees of acetylation were synthesized from cellulose extracted from corn stover. Membranes were prepared for the ultrafiltration process with pure polymers and blend form of CA utilizing a dioxane/acetone system. The membranes were characterized according to their transport properties. The blend form materials presented the best results for application in ultrafiltration experiments. M-TAC/DAC (corn stover triacetate and diacetate) and M-TAC/DAC-Rho (corn stover triacetate and Rhodia diacetate) presented rejection to egg albumin protein of 87.39% and 80.50%, respectively. Thus, MWCO of 45 kDa was determined for these materials.

Potentiometric determination of captopril in pharmaceutical formulations

A simple, precise, rapid and low-cost potentiometric method for captopril determination in pure form and in pharmaceutical preparations is proposed. Captopril present in tablets containing known quantity of drug was potentiometrically titrated in aqueous solution with NaOH using a glass pH electrode, coupled to an autotitrator. No interferences were observed in the presence of common components of the tablets as lactose, microcrystalline cellulose, croscarmellose sodium, starch and magnesium stearate. The analytical results obtained by applying the proposed method compared very favorably with those obtained by the United States Pharmacopoeia Standard procedure. Recovery of captopril from various tablet dosage formulations range from 98.0 to 102.0%.

Spectrophotometric determination of metronidazole through Schiff's base system using vanillin and PDAB reagents in pharmaceutical preparations

Two simple sensitive and reproducible spectrophotometric methods have been developed for the determination of metronidazole either in pure form or in their tablets. The proposed methods are based on the reduction of the nitro group to amino group of the drug. The reduction of metronidazole was carried out with zinc powder and 5 N hydrochloric acid at room temperature in methanol. The resulting amine was then subjected to a condensation reaction with aromatic aldehyde namely, vanillin and p-dimethyl amino benzaldehyde (PDAB) to yield yellow colored Schiff's bases. The formed Schiff's bases are quantified spectrophotometrically at their absorption maxima at 422 nm for vanillin and 494 nm for PDAB. Beer's law was obeyed in the concentration ranges 10 to 65 µg mL-1 and 5 to 40 µg mL-1 with a limit of detection (LOD) of 0.080 µg mL-1 and 0.090 µg mL-1 for vanillin and PDAB, respectively. The mean percentage recoveries were found to be 100.05 ± 0.37 and 99.01 ± 0.76 for the two methods respectively. The proposed methods were successfully applied to determine the metronidazole in their tablet formulations and the results compared favorably to that of reference methods. The proposed methods are recommended for quality control and routine analysis.

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.