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.

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.

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.

Influence of multi-phase phenomena on semibatch crystallization processes of aqueous solutions

Crystal properties, product quality and particle size are determined by the operating conditions in the crystallization process. Thus, in order to obtain desired end-products, the crystallization process should be effectively controlled based on reliable kinetic information, which can be provided by powerful analytical tools such as Raman spectrometry and thermal analysis. The present research work studied various crystallization processes such as reactive crystallization, precipitation with anti-solvent and evaporation crystallization. The goal of the work was to understand more comprehensively the fundamentals, phenomena and utilizations of crystallization, and establish proper methods to control particle size distribution, especially for three phase gas-liquid-solid crystallization systems. As a part of the solid-liquid equilibrium studies in this work, prediction of KCl solubility in a MgCl2-KCl-H2O system was studied theoretically. Additionally, a solubility prediction model by Pitzer thermodynamic model was investigated based on solubility measurements of potassium dihydrogen phosphate with the presence of non-electronic organic substances in aqueous solutions. The prediction model helps to extend literature data and offers an easy and economical way to choose solvent for anti-solvent precipitation. Using experimental and modern analytical methods, precipitation kinetics and mass transfer in reactive crystallization of magnesium carbonate hydrates with magnesium hydroxide slurry and CO2 gas were systematically investigated. The obtained results gave deeper insight into gas-liquid-solid interactions and the mechanisms of this heterogeneous crystallization process. The research approach developed can provide theoretical guidance and act as a useful reference to promote development of gas-liquid reactive crystallization. Gas-liquid mass transfer of absorption in the presence of solid particles in a stirred tank was investigated in order to gain understanding of how different-sized particles interact with gas bubbles. Based on obtained volumetric mass transfer coefficient values, it was found that the influence of the presence of small particles on gas-liquid mass transfer cannot be ignored since there are interactions between bubbles and particles. Raman spectrometry was successfully applied for liquid and solids analysis in semi-batch anti-solvent precipitation and evaporation crystallization. Real-time information such as supersaturation, formation of precipitates and identification of crystal polymorphs could be obtained by Raman spectrometry. The solubility prediction models, monitoring methods for precipitation and empirical model for absorption developed in this study together with the methodologies used gives valuable information for aspects of industrial crystallization. Furthermore, Raman analysis was seen to be a potential controlling method for various crystallization processes.

Evaluation of existing technologies in manufacturing of decorative solutions

Matkapuhelinvalmistajien välinen kilpailu kiristyy jatkuvasti. Tuotteiden ollessa teknisiltä ominaisuuksiltaan lähes samanvertaisia, asiakkaat alkavat kiinnittää huomiota myös puhelimen muihin ominaisuuksiin.Puhelimen koristeellisuudesta ja mandollisuudesta personoida matkapuhelin, on muodostumassa entistä tärkeämpiä tekijöitä puhelinvalmistajien välisessä kilpailussa. Asiakas ei myöskään ole valmis odottamaan puhelintaan, vaan haluaa puhelimensa nopesti. Lyhyt läpimenoaika on puhelinvalmistajille elintärkeä kilpailutekijä. Tämän työn tehtävänä on tutkija puhelinvalmistajien alihankkijan teknologisiamandollisuuksia laajentaa tuotevalikoimaansa vastaamaan tämän päivän tarpeita koristella matkaviestimiä. Teknologioioden sovellukset, Tuotantokustannukset, läpimenoajat ja teknologoiden riskit ovat tutkimuksen pääkohteet. Tavoitteena on saavuttaa käsitys kohdeyrityksen mandollisuuksista vastata asiakkaansa tarpeisiin olemassa olevilla teknologioilla ja niiden kombinaatioililla.

Freezing Point Depressions of Dilute Solutions of Alkali Metal Chlorides and Bromides

Freezing point depressions (¿Tf) of dilute solutions of several alkali metal chlorides and bromides were calculated by means of the best activity coefficient equations. In the calculations, Hückel, Hamer and Pitzer equationswere used for activity coefficients. The experimental ¿Tf values available in the literature for dilute LiCl, NaCl and KBr solutions can be predicted within experimental error by the Hückel equations used. The experimental ¿Tf values for dilute LiCl and KBr solutions can also be accurately calculated by corresponding Pitzer equations and those for dilute NaCl solutions by the Hamer equation for this salt. Neither Hamer nor Pitzer equations predict accurately the freezing points reported in the literature for LiBr and NaBr solutions. The ¿Tf values available for dilute solutions of RbCl, CsCl or CsBr are not known at the moment accurately because the existing data for these solutions are not precise. The freezing point depressions are tabulated in the present study for LiCl, NaCl and KBr solutions at several rounded molalities. The ¿Tf values in this table can be highly recommended. The activity coefficient equations used in the calculation of these values have been tested with almost allhigh-precision electrochemical data measured at 298.15 K.

PHOTOCATALYTIC OXIDATION OF AQUEOUS SOLUTIONS OF JET FUEL AND ICING INHIBITORS

The present paper is devoted to the results of experimental research undertaken into photocatalytical oxidation (PCO) of aqueous solutions of de-icing agents and aqueous extract of jet fuel. The report consists of introduction, literature review, description of materials and methods, discussion of results and conclusions. TiO2 was selected as a photocatalyst for the experiments with synthetic solutions of ethylene glycol, 2-ethoxyethanol and aqueous extract of jet fuel. To explain the PCO mechanisms affecting certain behaviour of de-icing agent under distinctive conditions, the following factors were studied: the impact of initial concentration of pollutant, the role of pH, the presence of tert-butanol as OH·-radicals scavenger and mineral admixtures. PCO under solar radiation performed in two ways: catalysed by irradiated TiO2 slurry or by TiO2 attached to buoyant hollow glass micro-spheres. Special attention was paid to the energy-saving PCO with reduced intensity mixing of the slurry. The effect of PCO was assessed by determination of residual chemical oxygen demand of solution (COD) and by measuring of concentration of glycols. The PCO process efficiency was assumed to be dependent on the TiO2 suspension fractional composition. Thus, the following effects of solutions’ media were viewed: presence of organic admixtures, pH influence, mixing mode during the PCO. The effects of mineral admixtures - Ca2+, Fe3+/2+, Mn2+, SO42- - that are often present in natural and wastewater systems or produced during the degradation of organic pollutants and which can affect the rate of PCO of de-icing agents, were also investigated.

Managing the Pricing of Integrated Solutions in Export Partnerships

Little research has been conducted to guide the management of marketing variables, such as pricing, in systems business context. Furthermore, given that international partnering has become a popular mode of operation for SMEs, the objective of the current thesis was to explore the scantly researched topic of managing the pricing of integrated solutions in an export partnership. Specifically, the thesis synthesizes literature findings from the three areas of export pricing, systems business, and export partnerships. The empirical section of the study consists of a qualitative single-case study of a Finnish systems integrator that has recently launched its export operations. Primary data was collected by conducting four interviews of the case company’s managers and by organizing one group interview session. The study findings indicate that a systems integrator’s pricing strategy in an export partnership can be very multidimensional and dependant on international pricing environment and partner characteristics, that an export partnership appears to have unique implications on a systems integrator’s pricing process, and that customer value –based pricing strategies might be particularly suited to pricing integrated solutions.

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.

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.

Purchasing Process of Industrial Solutions – Added Value, Difficulties and Good Practices

Purpose of this study is to clarify the industrial solutions purchasing process from purchaser companies’ point of view. Also customer’s view on value generating aspects and difficulties in purchases will be discussed as well as different purchas-ing entities where customers have ended up in their solution purchases. Current solution literature is mainly concentrated in supplier views and customer perspec-tive has been left without adequate attention. However, knowledge of the customer and the identification of customer need are at the core of a successful solution business. The focus of this thesis is on Finnish companies’ solution purchases that have been realized during last five years. Industrial solutions in this case are facto-ries or other large industrial plants. Industrial solutions’ purchasing process will be opened all the way from discovering the need until the start-up of the plant. Of in-terest is the customer experience of the success of the acquisition and the pur-chaser’s view on good practices allowing a successful procurement project.