Iron(III) as Lewis acid catalyst in organosilicon and carbonyl chemistry

Iron is one of the most common elements in the earth’s crust and thus its availability and economic viability far exceed that of metals commonly used in catalysis. Also the toxicity of iron is miniscule, compared to the likes of platinum and nickel, making it very desirable as a catalyst. Despite this, prior to the 21st century, the applicability of iron in catalysis was not thoroughly investigated, as it was considered to be inefficient and unselective in desired transformations. In this doctoral thesis, the application of iron catalysis in combination with organosilicon reagents for transformations of carbonyl compounds has been investigated together with insights into iron catalyzed chlorination of silanes and silanols. In the first part of the thesis, the synthetic application of iron(III)-catalyzed chlorination of silanes (Si-H) and the monochlorination of silanes (SiH2) using acetyl chloride as the chlorine source is described. The reactions proceed under ambient conditions, although some compounds need to be protected from excess moisture. In addition, the mechanism and kinetics of the chlorination reaction are briefly adressed. In the second part of this thesis a versatile methodology for transformation of carbonyl compounds into three different compound classes by changing the conditions and amounts of reagents is discussed. One pot reductive benzylation, reductive halogenation and reductive etherification of ketones and aldehydes using silanes as the reducing agent, halide source or cocatalyst, were investigated. Also the reaction kinetics and mechanism of the reductive halogenation of acetophenone are briefly discussed.

Tutustumiskierros terrorismintutkimukseen

Kirjallisuusarvostelu

Understanding Neolithic Southern Levant: case studies of archaeological semiosis in action

I undersökningen tillämpas Charles Sanders Peirces semiotik för en kritisk granskning av arkeologiska tolkningsprocesser. Enligt Peirce bygger all betydelsegivning på tecken, som kan vara teckningar, föremål, ord, byggkonstruktioner eller egentligen vad som helst. Ett tecken är tredimensionellt: ”objekt”, ”tecken” och ”tolkning”. I sina tidiga skrifter definierar han tre grundtyper för tecknet, Index, Icon och Symbol. De grundläggande definitionerna i Peirces semiotik blir till ett slags lins. När den placeras på skrifter av en arkeolog som uttolkar tecken, framträder deras inre uppbyggnad, motiveringar och logiska konsekvens klart. Att beakta är, att denna bok är lika lite avsedd att utgöra en systematisk klarläggning av den arkeologiska semiotiken, som en omfattande beskrivning av symboliken i det neolitiska Mellanöstern. Analysen är deskriptiv och inte avsedd att utvärdera tolkningarnas riktighet, utan enbart att klarlägga hur arkeologen kommit fram till dessa. Som objekt har valts neolitiska södra Levanten, där viktiga fynd gällande denna i mänsklighetens kulturhistoria så betydelsefulla skede har gjorts. Förhistorien är intressant med tanke på arkeologisk semiosis, eftersom uttolkaren av en symbol inte kan stöda sig på textfynd, utan måste på annat sätt upptäcka vad ett föremål eller en byggnad betytt för sin upphovsman. Att upptäcka en trovärdig betydelse är ofta en mycket svår och understundom rentav omöjlig uppgift. Efter att förhållandet mellan semiotik och arkeologi dryftats analyseras i boken John Garstangs och Kathleen M. Kenyons grundläggande tolkningar i Jeriko, Denise-Schmandt Besserats jämförande analyser för uttolkningen av \'Ain Ghazalis kranium, Michele A. Millers kontextuella analys i Jarmuk samt David Lewis-Williams’ starkt strukturalistiska analys av betydelsen av fynden i \'Ain Ghazal. Peirces semiotik har använts som stöd för arkeologin i mycket mindre utsträckning än F. de Saussures lingvistiska ja strukturalistiska semiotik. I Mellanöstern har man hittills inte alls gjort det. Ingen av de forskare som behandlas i boken hänvisar själv till semiotik eller tecken. Logiken i uttolkningen av dessa undersökningar är mycket invecklad, och de av Peirce gestaltade processerna för betydelsegivning visar sig härvidlag utgöra en ytterst klargörande kritisk apparat.

A tour through Sweden, Swedish-Lapland, Finland and Denmark. In a series of letters, illustrated with engravings : by Matthew Consett, esq.

P. 143-158 are misnumbered 142-157.

[Isabellan resitatiivi ja aaria Pensa alla patria]

Äänitetty radiosta.

Issuant views of hell in contemporary Anglo-American theology

This problem of hell is a specific form of the problem of evil that can be expressed in terms of a set of putatively incompatible statements: 1. An omnipotent God could create a world in which all moral agents freely choose life with God. 2. An omnibenevolent God would not create a world with the foreknowledge that some (perhaps a significant proportion) of God’s creatures would end up in hell. 3. An omniscient God would know which people will end up in hell. 4. Some people will end up forever in hell. Since the late twentieth century, a number of British and North American philosophical theologians, inspired by C.S. Lewis, have developed a new approach to answering the problem of hell. Very little work has been done to systematize this category of perspectives on the duration, quality, purpose and finality of hell. Indeed, there is no consensus among scholars as to what such an approach should be called. In this work, however, I call this perspective issuantism. Starting from the works of a wide range of issuantist scholars, I distill what I believe to be the essence of issuantist perspectives on hell: hell is a state that does not result in universal salvation and is characterized by the insistance that both heaven and hell must issue from the love of God, an affirmation of libertarian human freedom and a rejection of retributive interpretations of hell. These sine qua non characteristics form what I have labeled basic issuantism. I proceed to show that basic issuantism by itself does not provide an adequate answer to the problem of hell. The issuantist scholars themselves, however, recognize this weakness and add a wide range of possible supplements to their basic issuantism. Some of these supplemented versions of issuantism succeed in presenting reasonable answers to the problem of hell. One of the key reasons for the development of issuantist views of hell is a perceived failure on the part of conditionalists, universalists and defenders of hell as eternal conscious torment to give adequate answers to the problem of hell. It is my conclusion, however, that with the addition of some of the same supplements, versions of conditionalism and hell as eternal conscious torment can be advanced that succeed just as well in presenting answers to the problem of hell as those advanced by issuantists, thus rendering some of the issuantist critique of non-issuantist perspectives on hell unfounded.

Reusing repository technology for Cultural Heritage and Special Collections

Presentation at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.