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.

Promoting Growth in the Use of Bioenergy in Europe by Converting Existing Coal-Fired Power Plants to Biomass

Repowering existing power plants by replacing coal with biomass might offer an interesting option to ease the transition from fossil fuels to renewable energy sources and promote a fur-ther expansion of bioenergy in Europe, on account of the potential to decrease greenhouse gas emissions, as well as other pollutants (SOx, NOx, etcetera). In addition, a great part of the appeal of repowering projects comes from the opportunity to reuse the vast existing invest-ment and infrastructure associated with coal-based power generation. Even so, only a limited number of experiences with repowering are found. Therefore, efforts are required to produce technical and scientific evidence to determine whether said technology might be considered feasible for its adoption within European conditions. A detailed evaluation of the technical and economic aspects of this technology constitutes a powerful tool for decision makers to define the energy future for Europe. To better illustrate this concept, a case study is analyzed. A Slovakian pulverized coal plant was used as the basis for determining the effects on perfor-mance, operation, maintenance and cost when fuel is shifted to biomass. It was found that biomass fuel properties play a crucial role in plant repowering. Furthermore, results demon-strate that this technology offers renewable energy with low pollutant emissions at the cost of reduced capacity, relatively high levelized cost of electricity and sometimes, a maintenance-intensive operation. Lastly, regardless of the fact that existing equipment can be reutilized for the most part, extensive additions/modifications may be required to ensure a safe operation and an acceptable performance.

Three-dimensional modeling of biomass fuel flow in a circulating fluidized bed furnace

The reduction of greenhouse gas emissions in the European Union promotes the combustion of biomass rather than fossil fuels in energy production. Circulating fluidized bed (CFB) combustion offers a simple, flexible and efficient way to utilize untreated biomass in a large scale. CFB furnaces are modeled in order to understand their operation better and to help in the design of new furnaces. Therefore, physically accurate models are needed to describe the heavily coupled multiphase flow, reactions and heat transfer inside the furnace. This thesis presents a new model for the fuel flow inside the CFB furnace, which acknowledges the physical properties of the fuel and the multiphase flow phenomena inside the furnace. This model is applied with special interest in the firing of untreated biomass. An experimental method is utilized to characterize gas-fuel drag force relations. This characteristic drag force approach is developed into a gas-fuel drag force model suitable for irregular, non-spherical biomass particles and applied together with the new fuel flow model in the modeling of a large-scale CFB furnace. The model results are physically valid and achieve very good correspondence with the measurement results from large-scale CFB furnace firing biomass. With the methods and models presented in this work, the fuel flow field inside a circulating fluidized bed furnace can be modeled with better accuracy and more efficiently than in previous studies with a three-dimensional holistic model frame.

Comparison between freeze and spray drying to obtain powder Rubrivivax gelatinosus biomass

The use of colorants in products of animal origin is justified by the improvement in the color of foods since this attribute is considered a quality criterion. These additives can be produced using industrial effluents as substrates and appropriate organisms, such as Rubrivivax gelatinosus. Oxycarotenoids represent a class of carotenes responsible for the pigmentation of animals and vegetables. R. gelatinosus grows in fish industry effluent with the resulting production of a bacterial biomass containing oxycarotenoids. The purpose of this study was to compare the use of two drying processes - spray and freeze drying - to obtain powder biomass in terms of the process parameters (yield, productivity, and product recovery) and the product characteristics (color, proximate composition, and oxycarotenoids). No difference was detected in the yield between these techniques, while productivity was higher using spray drying. Higher product recovery and moisture were achieved with freeze drying, while ash was higher with spray drying. The freeze dried biomass was redder, darker and less saturated than the spray dried biomass. No difference in oxycarotenoids was detected between the biomasses. Although it results in lower recovery rate, spray drying was faster and more productive, and it provided the same yield as freeze drying, which makes it the method of choice for obtaining R. gelatinosus biomass.

Estimating microalgae Synechococcus nidulans daily biomass concentration using neuro-fuzzy network

In this study, a neuro-fuzzy estimator was developed for the estimation of biomass concentration of the microalgae Synechococcus nidulans from initial batch concentrations, aiming to predict daily productivity. Nine replica experiments were performed. The growth was monitored daily through the culture medium optic density and kept constant up to the end of the exponential phase. The network training followed a full 3³ factorial design, in which the factors were the number of days in the entry vector (3,5 and 7 days), number of clusters (10, 30 and 50 clusters) and internal weight softening parameter (Sigma) (0.30, 0.45 and 0.60). These factors were confronted with the sum of the quadratic error in the validations. The validations had 24 (A) and 18 (B) days of culture growth. The validations demonstrated that in long-term experiments (Validation A) the use of a few clusters and high Sigma is necessary. However, in short-term experiments (Validation B), Sigma did not influence the result. The optimum point occurred within 3 days in the entry vector, 10 clusters and 0.60 Sigma and the mean determination coefficient was 0.95. The neuro-fuzzy estimator proved a credible alternative to predict the microalgae growth.

Spirulina platensis: process optimization to obtain biomass

Spirulina platensis is a photoautotrophic mesophilic cyanobacterium. Its main sources of nutrients are nitrate, urea, and ammonium salts. Spirulina cultivation requires temperature, light intensity, and nutrient content control. This microalgae has been studied and used commercially due to its therapeutic and antioxidant potential. In addition, several studies have reported its ability to use CO2, its immune activity, and use as an adjuvant nutritive factor in the treatment of obesity. The objective of this study is the production of biomass of S. platensis using different rates of stirring, nitrogen source, amount of micronutrients, and luminosity. A 2(4) experimental design with the following factors: stirring (120 and 140 RPM), amount of nitrogen (1.5 and 2.5 g/L), amount of micronutrients (0,25 and 0,75 mL/L) (11 and 15 W), and luminosity was used. Fermentation was performed in a 500 mL conical flask with 250 mL of culture medium and 10% inoculum in an incubator with controlled stirring and luminosity. Fermentation was monitored using a spectrophotometer (560 nm), and each fermentation lasted 15 days. Of the parameters studied, luminosity is the one with the highest significance, followed by the amount of nitrogen and the interaction between stirring and micronutrients. Maximum production of biomass for 15 days was 2.70 g/L under the following conditions: luminosity15W; stirring, 120 RPM; source of nitrogen, 1.5 g/L; and micronutrients, 0.75 mL/L.

Biomass production by Arthrospira platensis under different culture conditions

In biotechnological processes, the culture media components are responsible for high costs and exert a strong influence on the cyanobacteria behavior. The objective of this study was to evaluate the Arthrospira platensis growth potential for biomass production under different cultivation conditions using an experimental design. Three factors that are important for cyanobacteria growth were evaluated: sodium bicarbonate (9 to 18 g/l), sodium nitrate (1.25 to 2.5 g/l), and irradiance (20 to 120 µmol photons/m2.s–1). The results showed that the concentration of NaNO3 in the A. platensis medium can be reduced, resulting in increased concentrations of biomass produced. There was a higher biomass production due to the increase in the concentration of NaHCO3 and irradiance, mainly when these two factors varied tending towards the highest values studied. The results demonstrate the potential to produce Arthrospira platensis with lower costs and effluent generation without affecting cultivation performance.

Water chemistry management for future large experimental facilities

The thesis focuses on the water chemistry of the experimental test facilities and their reference VVER reactors. The main objective of the thesis is to provide recommendations for water chemistry management for laboratory facilities (VEERA, PACTEL) simulating the VVERs and for the large future facilities of the Lappeenranta University of Technology. In the beginning, the concept of nuclear power generation and the applicability of the nuclear power usage is discussed. Next, different water chemistry and water purification systems in primary and secondary circuits currently used at the power plant have been outlined. Also the construction geometry and design of test facilities PACTEL and VEERA, as well as the operation principles of their main equipment has been described. Finally, the appropriate water chemistry and water treatment system have been proposed for the existing and future experimental facilities of LUT.

Internet-markkinoinnin kehittäminen: Case Outotec HSC Chemistry

Kandidaatintyö käsittelee ohjelmistojen markkinointia internetissä ja markkinoinnin mittaamista. Työssä esitellään internetin eri markkinointikanavat käsitellen niiden toteutustapoja, vahvuuksia ja heikkouksia sekä kustannuksia. Internet-markkinoinnin mittaamisesta käsitellään erilaisia tunnuslukuja sekä mittaamisen käyttökohteita. Työ on pääasiassa kirjallisuuskatsaus, mutta samalla myös case: työssä käsitellään Outotecin toimeksiannosta sen kehittämän HSC Chemistry -ohjelmiston markkinointia internetissä. Työn tuloksissa suositellaan HSC Chemistrylle sopivia markkinointikanavia ja niiden kustannuksia. Lisäksi arvioidaan käsiteltyjen mittaamistapojen soveltuvuutta ohjelmiston tapauksessa.

An analysis of the photoelectron and Rydberg states of formaldehyde /|nby Carol R. Lessard. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

Although it is generally accepted that Rydberg orbitals are very large and diffuse, and that electron promotion to a Rydberg orbital is not too different from ionization of the molecule, analysis of the two types of transitions proves otherwise. The photoelectron spectrum of the 2B2 (n) ion has very little vibrational structure attached to the origin band; on the other hand, several of the Rydberg transitions which involve the promotion of the n(bZ) electron exhibit a great deal of vibrational activity. In particular, the members of the n=3 Rydberg\ series interact with and perturb each other through pseudo-Jahn-Teller vibronic coupling. The vacuum ultraviolet spectrum contains a number of features which are difficult to explain, and two unusually sharp bands can only be identified as representing some form of electron promotion in formaldehyde.

A study of thermal decompositions of an allylic hydroperoxide /|nby Thomas A. McCarrick. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The thermal decomposition of 2,3-di~ethy l - J-hydr operox y- 1 - butene , p r epared f rol") singl e t oxygen, has been studied i n three solvents over the tempe r a ture r ange from 1500e to l o00e and t!1e i 111 t ial ~oncentrfttl nn r Ange from O. 01 M to 0.2 M. Analys i s of the kine tic data ind ica te s i nduced homolysis as the n ost probRble mode of d e composition, g iving rise to a 3/2 f S order dependence upon hy d.roperoxide concent :r8.tl on . Experimental activation e nergies for the decomposition were f ound to be between 29.5 kcsl./raole and 30.0 k cal./mole .• \,iith log A factors between 11 . 3 and 12.3. Product studies were conducted in R variety of solvents a s well as in the pr esence of a variety of free r adical initiators . Investigation of the kinetic ch a in length indicated a chain length of about fifty. A degenerat i ve chain branching mechanism 1s proposed which predicts the multi t ude of products which Rre observed e xperimentally as well as giving activation energies and log A factors si~il a r to those found experimentally .

Reduced local energy calculations on X¹Sigmaâ ½gHâ and 1¹S He /|nGerald F. Thomas. -- 260 St. Catharines [Ont.] : Dept. of Chemistry, Brock University,

The one-electron reduced local energy function, t ~ , is introduced and has the property < tL)=(~>. It is suggested that the accuracy of SL reflects the local accuracy of an approximate wavefunction. We establish that <~~>~ <~2,> and present a bound formula, E~ , which is such that where Ew is Weinstein's lower bound formula to the ground state. The nature of the bound is not guaranteed but for sufficiently accurate wavefunctions it will yield a lower bound. ,-+ 1'S I I Applications to X LW Hz. and ne are presented.

Some aspects of the chemistry of Reissert compounds / |nDurga Prasad Aysola. -- 260 St. Catharines [Ont. : s. n.],

1-(0- and m-Ohlorobenzoyl)isoquinolines have been synthesized by two routes involving Reissert compounds. One route involves condensation of 2-benzoyl-l,2-dihydroisoquinaldonitrile with the appropriate chlorobenzaldehyde and the second involves rearrangement of the appropriate Z-(chlorobenzoyl)-l,Z-dihydroisoquinaldonitrile under basic conditions. The action of potassamide in anhydrous liquid ammonia on both ketones gave unexpectedly N-(l-isoquinolyl)benzamide (67) as the major product and the use of dibenzo-18-crown-6-ether 98% substantially improved the yd..e.ld in the case of l-chloroketone. This amide (67) exhibits unusual hydrogen bonding. 1-(o-chlorobenzoyl)-6,7-dimethoxyisoquinoline (79) was prepared in very s,amll quantities by the route involving condensation of 2-benzoyll, Z-dihydro-6,7-dimethoxyisoquinaldonitrile with o-chlorobenzaldehyde. The poor yields are due to the instability of the anion of 2-benzoyl1, Z-dihydro-6,7-dimethoxyisoquinaldonitrile. Attempted preparation of the ketone (79) by rearrangement of 2-(o-chlorobenzoyl)-l,2-dihydro6,7- dimethoxyisoquinaldonitrile under basic conditions yielded the start~ng material (Reissert compound) and 6,7-dimethoxyisoquinoline. The action of potassamide in anhydrous liquid ammonia on l-(o-bromo-4,5-dimethoxybenzoyl)isoquinoline (85), which was prepared by the route involving the condensation of 2-benzoyl-l,4-dihydroisoquinaldonitrile with o-bromo-4,5-dimethoxybenzaldehyde, gave two products, which have not yet been identified. The ketone (85) and its precursors are interest~ng in that their 20 eV and 70 eV mass spectra do not show molecular ions.

Some aspects of the chemistry of 1, 3, 4 - Thiadiazolium salts and related compounds

The work described in this thesis has been divided into seven sections. The first section involves the preparation of N'-acyl-N'-arylN- benzothiohydrazides by the acylation of N'-aryl-N-benzothiohydrazides and is followed by a brief discussion of their possible conformation in solution. The second section deals with the preparation of 1,3,4-thiadiazolium salts by the action of perchloric acid/acetic anhydride on N'-acylN'- aryl-N-benzothiohydrazides and also by the reaction of N'-arylN- benzothiohydrazides with nitriles in an acidic medium. The preparation of 2-methylthio-I,3,4-thiadiazolium methosulfate by methylating the corresponding thione is also described. The third section deals with the reaction of 2-phenyl- and 2-methyl-I,3,4-thiadiazolium salts with alcohols in the presence of base. The stability and spectra of these compounds are discussed. Treatment of the 2-methyl-I,3,4-thiadiazolium salt with base was found to give rise to a dimeric anhydrobase and evidence supporting its structure is given. The anhydrobase could be trapped by a variety of acylating and thioacylating agents before dimerization occurred. In the fourth section, the reaction of N'-acyl-N'-aryl-N-benzothiohydrazides with a variety of acid anhydrides is described. These compounds were found to be identical with those obtained by acylating the anhydrobase. The mass spectral fragmentation of these compounds is described and the anomolous product obtained upon thiobenzoylation of 3-methyl-l-phenyl-pyrazal-5-one is also discussed. The fifth section deals with thioacyl derivatives of the anhydrobase which were prepared by the action of phosphorus pentasulfide upon the oxygen analogues and also obtained as the major product of the reaction of thioacetic acid with compounds related to N'-aryl-N-benzothiohydrazides. The mass spectra and p.m.r. spectra of these compounds are discussed. In the sixth section, the reaction of the 2-methylthio-l,3,4- thiadiazolium salt with active methylene compounds to give acyl and diacyl derivatives of the anhydrobase is described. Some aspects of these compounds are discussed. The seventh section describes the synthesis of ncyanine~' type dyes incorporating the l,3,4-thiadiazole ring and their spectra are briefly discussed.

The chemistry of heterocyclic methine bases and of their acyl and thioacyl derivatives

The work described in this thesis has been dtvided into six sections . The first section involves the reaction of 3,5-diphenyl-2-methyl-l,3,4-oxadiazolium perchlorate with acetic and benzoic anhydrides. The second section deals with the preparation and reactions of 1,3,4-thia diazolium salts. Some monomeric 1,3,4-thiadiazoline methine bases have also been prepared by reacting 1,3,4-thia d iaz ol ium s al t s with concen trated ammonium hydroxide solution. Variable temperature p.m.r. of 2-(3-acetylacetonylidene)-3,5-diphenyl-A4 -1,3,4-thiadiazoline has also been described. The third section deals with prepar a tion and reactions of some compounds in benzoxazole series. The fourth section deals with the prep a ration and reactions of N-alkyl-2-methylbenzothi azolium salts with base , a nd with some a cetylating and thioacetylating agents. Treatment of 2,3-dimethylbenzothiazolium iodide and of 3-ethyl-2-methylbenzothia zolium iodide with base wa s found to give the corresponding dimeric methine b a ses and evidence supporting their structure is also given. Thiol acetic acid was found to exchange 0 for S in its reactions with 2-acetonylidene-3-methylbenzothiazoline and 2-acetophenonylidene-3-methylbenzothi a zoline. (ii) In th e fifth section, the r eactions of 2,3-dimethylbenzselenazolium iodide with a variety of ac e tylating and thioacetylating agents has been described. The treatment of 2,3-dimethylbenzselenazolium iodide with base was found to give rise to a dimeric methine base and evidence supporting its structure is also given. The reactions of this dimeric methine b a se with benzoic anhydride and phenylisothiocyanate have also been described. The sixth section deals with the preparation and reactions of l-alkyl-2-methylquinolinium salts. Treatment of 1,2-dimethylquinolinium iodide and l-ethyl-2-methylquinolinium iodide was found to give the corresponding monomeric methine bases and evidence supporting their structure is also given. The E-type geometry of the olefinic bond in 2-acetonylidene-l-methylquinoline has been established on the basis of an N.O.E. experiment.