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.

The Process of Greening Cycle as Method of Operative Environmental

The structural change of society from product-based business to service- and further to need-based business has caused the fact that work for environmental issues has spread from conventional factories and environmentally harmful production to concern services and offices as well. Almost every company has an office, so a relatively small environmental burden caused by an individual office grows remarkable already at the state level and globally even more. Motivation to work for environmental issues in an individual office could be challenging even without the fact that wasted environmental impacts bound also wasted costs. Besides cost savings, a concretely greener image of a company has its value in the B2Cas well as in the B2B-field. Consumers and clients are more and more conscious of environmental issues and demand concrete actions instead of speeches, good thoughts and meaningless certifications. Internal work for environmental issues at a strategy level is not sufficient, so operational environmental management is needed for changing old practices. This research is about the effects of operative environmental management on the greening process of an office-based business. The research is outlined to concern the operative work in the office including field sales. Target was to concretely lower the environmental impacts of Lyreco Finland and to find cost savings directly by changing the operative practices in the office and also indirectly by affecting the level of environmental knowledge of the personnel. During the greening process, the aim was also to create concrete arguments for marketing as well. The circle of greening process, which was especially created for this diploma work, was used as a method. The circle divides a year to themes and sections separated by factors of environmental impacts. Separation is based on Brett Wills’ thoughts of seven green wastes (Wills, Brett. The Green Intensions. 2009) and follows it uneasily. The circle aimed at ensuring evolutionary growth of knowledge instead of being revolutionary in the changing process. Committing personnel to the process from its start by asking ideas from them and giving them clear directions was an important part of the research of operative management. Because of working from distance, communication with personnel was operated by frequent training days and weekly greening notes via emails and intranet. Also availability for communication was an important task because of the telecommuting. Research results of this work show that operative environmental management in an officebased business today is mostly management of change. When the strategic environmental friendliness is taken into a concrete level, the most important individual factor is motivating the operating personnel. Research shows that evolutionary change is found being an efficient way to make a change. Also understanding one´s own impact on the environmental burden and on the whole greening process clearly motivates the personnel. Results show that in the operative realization of the greening process, clear directions of new working practices, being as concrete as possible, and committing personnel to follow them make the process more effective. The operative environmental management and the cycle of the greening process decrease the environmental burden and save costs. The concrete results could be used as believable arguments in marketing and therefore exploited in communication with interest groups. Commitment of the management is also one of the key factors of success in the greening process. In this research, changes in the business field by a company trade took the focus of the management away from the greening process and made the process more inefficient by decreasing the amount of training days. The circle of greening process will be used as a tool in the future, as well, and therefore it will help observe environmental impacts of a company and increase sustainable development. Commitment of management to the evolutionary environmental work helps the operating personnel lower environmental impacts, decrease costs and build a concretely greener image.

Optimization as a method of search engine marketing

This study is dedicated to search engine marketing (SEM). It aims for developing a business model of SEM firms and to provide explicit research of trustworthy practices of virtual marketing companies. Optimization is a general term that represents a variety of techniques and methods of the web pages promotion. The research addresses optimization as a business activity, and it explains its role for the online marketing. Additionally, it highlights issues of unethical techniques utilization by marketers which created relatively negative attitude to them on the Internet environment. Literature insight combines in the one place both technical and economical scientific findings in order to highlight technological and business attributes incorporated in SEM activities. Empirical data regarding search marketers was collected via e-mail questionnaires. 4 representatives of SEM companies were engaged in this study to accomplish the business model design. Additionally, the fifth respondent was a representative of the search engine portal, who provided insight on relations between search engines and marketers. Obtained information of the respondents was processed qualitatively. Movement of commercial organizations to the online market increases demand on promotional programs. SEM is the largest part of online marketing, and it is a prerogative of search engines portals. However, skilled users, or marketers, are able to implement long-term marketing programs by utilizing web page optimization techniques, key word consultancy or content optimization to increase web site visibility to search engines and, therefore, user’s attention to the customer pages. SEM firms are related to small knowledge-intensive businesses. On the basis of data analysis the business model was constructed. The SEM model includes generalized constructs, although they represent a wider amount of operational aspects. Constructing blocks of the model includes fundamental parts of SEM commercial activity: value creation, customer, infrastructure and financial segments. Also, approaches were provided on company’s differentiation and competitive advantages evaluation. It is assumed that search marketers should apply further attempts to differentiate own business out of the large number of similar service providing companies. Findings indicate that SEM companies are interested in the increasing their trustworthiness and the reputation building. Future of the search marketing is directly depending on search engines development.

Development of an environmentally friendly method of starch oxidation by hydrogen peroxide and a complex water-soluble Iron catalyst

Oxidized starch is a key component in the paper industry, where it is used as both surfacing sizer and filler. Large quantities are annually used for this purpose; however, the methods for the oxidation are not environmentally friendly. In our research, we have studied the possibility to replace the harmful oxidation agents, such as hypochlorite or iodates and transition metal catalysts, with a more environmentally friendly oxidant, hydrogen peroxide (H2O2), and a special metal complex catalyst (FePcS), of which only a small amount is needed. The work comprised batch and semi-batch studies by H2O2, ultrasound studies of starch particles, determination of low-molecular by-products and determination of the decomposition kinetics of H2O2 in the presence of starch and the catalyst. This resulted in a waste-free oxidation method, which only produces water and oxygen as side products. The starch oxidation was studied in both semi-batch and batch modes in respective to the oxidant (H2O2) addition. The semi-batch mode proved to yield a sufficient degree of substitution (COOH groups) for industrial purposes. Treatment of starch granules by ultrasound was found to improve the reactivity of starch. The kinetic results were found out to have a rather complex pattern – several oxidation phases were observed, apparently due to the fact that the oxidation reaction in the beginning only took place on the surface, whereas after a prolonged reaction time, partial degradation of the solid starch granules allowed further reaction in the interior parts. Batch-mode experiments enabled a more detailed study of the mechanisms of starch in the presence of H2O2 and the catalyst, but yielded less oxidized starch due to rapid decomposition of H2O2 due to its high concentrations. The effect of the solid-liquid (S/L) ratio in the reaction system was studied in batch experiments. These studies revealed that the presence of the catalyst and the starch enhance the H2O2 decomposition.

Excavation-drier method of energy-peat extraction reduces long-term climatic impact

Climatic impacts of energy-peat extraction are of increasing concern due to EU emissions trading requirements. A new excavation-drier peat extraction method has been developed to reduce the climatic impact and increase the efficiency of peat extraction. To quantify and compare the soil GHG fluxes of the excavation drier and the traditional milling methods, as well as the areas from which the energy peat is planned to be extracted in the future (extraction reserve area types), soil CO2, CH4 and N2O fluxes were measured during 2006–2007 at three sites in Finland. Within each site, fluxes were measured from drained extraction reserve areas, extraction fields and stockpiles of both methods and additionally from the biomass driers of the excavation-drier method. The Life Cycle Assessment (LCA), described at a principal level in ISO Standards 14040:2006 and 14044:2006, was used to assess the long-term (100 years) climatic impact from peatland utilisation with respect to land use and energy production chains where utilisation of coal was replaced with peat. Coal was used as a reference since in many cases peat and coal can replace each other in same power plants. According to this study, the peat extraction method used was of lesser significance than the extraction reserve area type in regards to the climatic impact. However, the excavation-drier method seems to cause a slightly reduced climatic impact as compared with the prevailing milling method.

Cleaning of ceramic filter plates

In this thesis, cleaning of ceramic filter plates clogged by iron oxides was studied. Oxalic acid is considered as the most effective cleaning agent for the plates fouled by iron oxides, but when using oxalic acid, sparingly soluble calcium oxalate may be formed and it can blind the filter media. Suitability of another chemical for cleaning the plates clogged by iron oxides was studied in this thesis. The literature part was mostly about the properties of the chemical, about its reactions, industrial uses, safety issues etc. In the experimental part, the efficiency of the chemical for cleaning of the ceramic plates clogged by iron oxides was studied. Two kinds of plates were used in the experiments; the others were clogged by hematite and the others by magnetite. Both soaking and flow-through experiments were done. A suitable concentration, pH and temperature were tried to find in the experiments. Also the effect of ultrasound was studied. The efficiency of the cleaning was examined by measuring the permeability of the plates during the experiments. ICP-OES analysis was performed for determining the amount of dissolved iron in the washing solution. Some experiments were also done with oxalic acid. The results from the oxalic acid experiments were compared to the results from the experiments with the other chemical. In the experiments with the other chemical, the permeability increased more and the amounts of dissolved iron were larger. According to the results from the experiments, the method of application of the washing solutions had an impact on the washing results.

Adaptation of TRIZ Method for Problem Solving in Process Engineering

TRIZ is one of the well-known tools, based on analytical methods for creative problem solving. This thesis suggests adapted version of contradiction matrix, a powerful tool of TRIZ and few principles based on concept of original TRIZ. It is believed that the proposed version would aid in problem solving, especially those encountered in chemical process industries with unit operations. In addition, this thesis would help fresh process engineers to recognize importance of various available methods for creative problem solving and learn TRIZ method of creative problem solving. This thesis work mainly provides idea on how to modify TRIZ based method according to ones requirements to fit in particular niche area and solve problems efficiently in creative way. Here in this case, the contradiction matrix developed is based on review of common problems encountered in chemical process industry, particularly in unit operations and resolutions are based on approaches used in past to handle those issues.

Utilization of steelmaking waste materials for production of calcium carbonate (CaCO3)

The steel industry produces, besides steel, also solid mineral by-products or slags, while it emits large quantities of carbon dioxide (CO2). Slags consist of various silicates and oxides which are formed in chemical reactions between the iron ore and the fluxing agents during the high temperature processing at the steel plant. Currently, these materials are recycled in the ironmaking processes, used as aggregates in construction, or landfilled as waste. The utilization rate of the steel slags can be increased by selectively extracting components from the mineral matrix. As an example, aqueous solutions of ammonium salts such as ammonium acetate, chloride and nitrate extract calcium quite selectively already at ambient temperature and pressure conditions. After the residual solids have been separated from the solution, calcium carbonate can be precipitated by feeding a CO2 flow through the solution. Precipitated calcium carbonate (PCC) is used in different applications as a filler material. Its largest consumer is the papermaking industry, which utilizes PCC because it enhances the optical properties of paper at a relatively low cost. Traditionally, PCC is manufactured from limestone, which is first calcined to calcium oxide, then slaked with water to calcium hydroxide and finally carbonated to PCC. This process emits large amounts of CO2, mainly because of the energy-intensive calcination step. This thesis presents research work on the scale-up of the above-mentioned ammonium salt based calcium extraction and carbonation method, named Slag2PCC. Extending the scope of the earlier studies, it is now shown that the parameters which mainly affect the calcium utilization efficiency are the solid-to-liquid ratio of steel slag and the ammonium salt solvent solution during extraction, the mean diameter of the slag particles, and the slag composition, especially the fractions of total calcium, silicon, vanadium and iron as well as the fraction of free calcium oxide. Regarding extraction kinetics, slag particle size, solid-to-liquid ratio and molar concentration of the solvent solution have the largest effect on the reaction rate. Solvent solution concentrations above 1 mol/L NH4Cl cause leaching of other elements besides calcium. Some of these such as iron and manganese result in solution coloring, which can be disadvantageous for the quality of the PCC product. Based on chemical composition analysis of the produced PCC samples, however, the product quality is mainly similar as in commercial products. Increasing the novelty of the work, other important parameters related to assessment of the PCC quality, such as particle size distribution and crystal morphology are studied as well. As in traditional PCC precipitation process, the ratio of calcium and carbonate ions controls the particle shape; a higher value for [Ca2+]/[CO32-] prefers precipitation of calcite polymorph, while vaterite forms when carbon species are present in excess. The third main polymorph, aragonite, is only formed at elevated temperatures, above 40-50 °C. In general, longer precipitation times cause transformation of vaterite to calcite or aragonite, but also result in particle agglomeration. The chemical equilibrium of ammonium and calcium ions and dissolved ammonia controlling the solution pH affects the particle sizes, too. Initial pH of 12-13 during the carbonation favors nonagglomerated particles with a diameter of 1 μm and smaller, while pH values of 9-10 generate more agglomerates of 10-20 μm. As a part of the research work, these findings are implemented in demonstrationscale experimental process setups. For the first time, the Slag2PCC technology is tested in scale of ~70 liters instead of laboratory scale only. Additionally, design of a setup of several hundreds of liters is discussed. For these purposes various process units such as inclined settlers and filters for solids separation, pumps and stirrers for material transfer and mixing as well as gas feeding equipment are dimensioned and developed. Overall emissions reduction of the current industrial processes and good product quality as the main targets, based on the performed partial life cycle assessment (LCA), it is most beneficial to utilize low concentration ammonium salt solutions for the Slag2PCC process. In this manner the post-treatment of the products does not require extensive use of washing and drying equipment, otherwise increasing the CO2 emissions of the process. The low solvent concentration Slag2PCC process causes negative CO2 emissions; thus, it can be seen as a carbon capture and utilization (CCU) method, which actually reduces the anthropogenic CO2 emissions compared to the alternative of not using the technology. Even if the amount of steel slag is too small for any substantial mitigation of global warming, the process can have both financial and environmental significance for individual steel manufacturers as a means to reduce the amounts of emitted CO2 and landfilled steel slag. Alternatively, it is possible to introduce the carbon dioxide directly into the mixture of steel slag and ammonium salt solution. The process would generate a 60-75% pure calcium carbonate mixture, the remaining 25-40% consisting of the residual steel slag. This calcium-rich material could be re-used in ironmaking as a fluxing agent instead of natural limestone. Even though this process option would require less process equipment compared to the Slag2PCC process, it still needs further studies regarding the practical usefulness of the products. Nevertheless, compared to several other CO2 emission reduction methods studied around the world, the within this thesis developed and studied processes have the advantage of existing markets for the produced materials, thus giving also a financial incentive for applying the technology in practice.

Dual light barrier method for six degrees of freedom tool center point calibration of an industrial robot

Tool center point calibration is a known problem in industrial robotics. The major focus of academic research is to enhance the accuracy and repeatability of next generation robots. However, operators of currently available robots are working within the limits of the robot´s repeatability and require calibration methods suitable for these basic applications. This study was conducted in association with Stresstech Oy, which provides solutions for manufacturing quality control. Their sensor, based on the Barkhausen noise effect, requires accurate positioning. The accuracy requirement admits a tool center point calibration problem if measurements are executed with an industrial robot. Multiple possibilities are available in the market for automatic tool center point calibration. Manufacturers provide customized calibrators to most robot types and tools. With the handmade sensors and multiple robot types that Stresstech uses, this would require great deal of labor. This thesis introduces a calibration method that is suitable for all robots which have two digital input ports free. It functions with the traditional method of using a light barrier to detect the tool in the robot coordinate system. However, this method utilizes two parallel light barriers to simultaneously measure and detect the center axis of the tool. Rotations about two axes are defined with the center axis. The last rotation about the Z-axis is calculated for tools that have different width of X- and Y-axes. The results indicate that this method is suitable for calibrating the geometric tool center point of a Barkhausen noise sensor. In the repeatability tests, a standard deviation inside robot repeatability was acquired. The Barkhausen noise signal was also evaluated after recalibration and the results indicate correct calibration. However, future studies should be conducted using a more accurate manipulator, since the method employs the robot itself as a measuring device.

Synthesis of Short Oligonucleotides on a Soluble Support by the Phosphoramidite Method

In the last decades, the chemical synthesis of short oligonucleotides has become an important aspect of study due to the discovery of new functions for nucleic acids such as antisense oligonucleotides (ASOs), aptamers, DNAzymes, microRNA (miRNA) and small interfering RNA (siRNA). The applications in modern therapies and fundamental medicine on the treatment of different cancer diseases, viral infections and genetic disorders has established the necessity to develop scalable methods for their cheaper and easier industrial manufacture. While small scale solid-phase oligonucleotide synthesis is the method of choice in the field, various challenges still remain associated with the production of short DNA and RNA-oligomers in very large quantities. On the other hand, solution phase synthesis of oligonucleotides offers a more predictable scaling-up of the synthesis and is amenable to standard industrial manufacture techniques. In the present thesis, various protocols for the synthesis of short DNA and RNA oligomers have been studied on a peracetylated and methylated β-cyclodextrin, and also on a pentaerythritol-derived support. On using the peracetylated and methylated β-cyclodextrin soluble supports, the coupling cycle was simplified by replacement of the typical 5′-O-(4,4′-dimethoxytrityl) protecting group with an acid-labile acetal-protected 5′-O-(1-methoxy-1-methylethyl) group, which upon acid-catalyzed methanolysis released easily removable volatile products. For this reason monomeric building blocks 5′-O-(1-methoxy-1-methylethyl) 3′-(2-cyano-ethyl-N,N-diisopropylphosphoramidite) were synthesized. Alternatively, on using the precipitative pentaerythritol support, novel 2´-O-(2-cyanoethyl)-5´-O-(1-methoxy-1-methylethyl) protected phosphoramidite building blocks for RNA synthesis have been prepared and their applicability by the synthesis of a pentamer was demonstrated. Similarly, a method for the preparation of short RNAs from commercially available 5´-O-(4,4´-dimethoxytrityl)-2´-O-(tert-butyldimethyl-silyl)ribonucleoside 3´-(2-cyanoethyl-N,N-diisopropylphosphoramidite) building blocks has been developed

A modified nominal stress method for fatigue assessment of steel plates with thermally cut edges

Thermal cutting methods, are commonly used in the manufacture of metal parts. Thermal cutting processes separate materials by using heat. The process can be done with or without a stream of cutting oxygen. Common processes are Oxygen, plasma and laser cutting. It depends on the application and material which cutting method is used. Numerically-controlled thermal cutting is a cost-effective way of prefabricating components. One design aim is to minimize the number of work steps in order to increase competitiveness. This has resulted in the holes and openings in plate parts manufactured today being made using thermal cutting methods. This is a problem from the fatigue life perspective because there is local detail in the as-welded state that causes a rise in stress in a local area of the plate. In a case where the static utilization of a net section is full used, the calculated linear local stresses and stress ranges are often over 2 times the material yield strength. The shakedown criteria are exceeded. Fatigue life assessment of flame-cut details is commonly based on the nominal stress method. For welded details, design standards and instructions provide more accurate and flexible methods, e.g. a hot-spot method, but these methods are not universally applied to flame cut edges. Some of the fatigue tests of flame cut edges in the laboratory indicated that fatigue life estimations based on the standard nominal stress method can give quite a conservative fatigue life estimate in cases where a high notch factor was present. This is an undesirable phenomenon and it limits the potential for minimizing structure size and total costs. A new calculation method is introduced to improve the accuracy of the theoretical fatigue life prediction method of a flame cut edge with a high stress concentration factor. Simple equations were derived by using laboratory fatigue test results, which are published in this work. The proposed method is called the modified FAT method (FATmod). The method takes into account the residual stress state, surface quality, material strength class and true stress ratio in the critical place.