A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

The functional fit between collaborative software and work systems:Qualification of work system needs to software functionality

The study develops an approach that tries to validate software functionality to work systems needs in SMEs. The formulated approach is constructed by using a SAAS based software i.e., work collaboration service (WCS), and SMEs as the elements of study. Where the WCS’s functionality is qualified to the collaboration needs that exist in operational and project work within SMEs. For this research constructivist approach and case study method is selected because the nature of the current study requires an in depth study of the work collaboration service as well as a detailed study of the work systems within different enterprises. Four different companies are selected in which fourteen interviews are conducted to gather data pertaining. The work systems method and framework are used as a central part of the approach to collect, analyze and interpret the enterprises work systems model and the underlying collaboration needs on operational and project work. On the other hand, the functional model of the WCS and its functionality is determined from functional model analysis, software testing, documentation and meetings with the service vendor. The enterprise work system model and the WCS model are compared to reveal how work progression differs between the two and make visible unaddressed stages of work progression. The WCS functionality is compared to work systems collaboration needs to ascertain if the service will suffice the needs of the project and operational work under study. The unaddressed needs provide opportunities to improve the functionality of the service for better conformity to the needs of enterprise and work. The results revealed that the functional models actually differed in how operational and project work progressed within the stages. WCS shared similar stages of work progression apart from the stages of identification and acceptance, and progress and completion stages were only partially addressed. Conclusion is that the identified unaddressed needs such as, single point of reference, SLA and OLA inclusion etc., should be implemented or improved within the WCS at appropriate stages of work to gain better compliance of the service to the needs of the enterprise an work itself. The developed approach can hence be used to carry out similar analysis for the conformance of pre-built software functionality to work system needs with SMEs.

Motives and barriers for engaging in collaborative consumption in Finland

In this thesis the consumers’ expected motives and barriers for engaging in collaborative consumption in Finland are studied. The phenomenon is observed through the lens of consumer theory and it is connected to the context using Hofstede’s 6-D model. The phenomenon is new and there are almost no recorded results in the background research, and when considering the limitations of this study, there are no results at all. Therefore, combining different kinds of literature, as well as taking along consumer theory and Hofstede’s model that explains cultural factors, it was possible to compile a comprehensive general view of the present state of the phenomenon. The actual study was conducted using qualitative methods and the solution was sought collecting data from six in-depth interviews with interviewees having experience from using, or offering resources, or both. According to the results, the primary motive in all modes of consumption was economic. Anti-materialism, anti-consumption, and expanding lifestyle were another a bit more general motives. Perceived barriers were, especially as a new result, the amount of trouble one has to see and in single modes, a lack of trust, the used platform and too expensive prices.

Collaborative learning in a Japanese as a foreign language classroom /

This study examined the influence of training on Asian learners' beliefs, interaction, and attitudes during collaborative learning (CL) and explored the processes of their CL in pairs. The literature contains few studies on the effect of collaborative training in language learning. In addition, it shows gaps between SLA theory and practice resulting from learners' cultural differences. Although second/subsequent language acquisition (SLA) theory assumes that CL contributes to language learning, implementing CL in a multicultural classroom is often considered to be unsuccessful by teachers. The research questions designed to address this gap explore: (a) the extent to which tra~ng affects Asian learners' attitudes towards and interaction during CL; (b) how Asian learners accomplish collaborative tasks in pairs. In the quasi-experimental research design, the learners in the treatment group received special training in CL for 5 weeks while the learners in the comparison group did not receive similar training. Data were collected from 45 McMaster University students through pre- and posttests, pre- and postintervention questionnaires, student information, and informal classroom observations. To detennine the influence of training, the frequency of communication units (c-units), Language Related Episodes (LREs), Collaborative Dialogue (CD) from audio-taped data, and the fmal draft scores were compared between pre- and posttests. The learners' pre- and postintervention questionnaires were also compared. Transcripts from audio-taped data, students' information, their responses and comments from questionnaires, and informal observations served to investigate the processes of Asian learners' CL. Overall, this study found that training had significant influence on the frequency of c-units and CD, and considerable impact on the draft scores, although little influence on the frequency of LREs was observed. The results from the questionnaires in the treatment group showed positive changes in the learners' beliefs on pair work after training. On the other hand, analyses of the transcription data showed that the learners did not conduct enough discussion for a resolution of problems with peers. In conclusion, results suggested the need for teacher intervention, a longer period of collaborative training, and an implementation of self-evaluation into the course grade to encourage the learners to succeed in collaborative learning.

The quality of the mother-child relationship during collaborative problem solving /

The quality of the mother-child relationship was examined in relation to joint planning, maternal teaching strategies, maternal emotional support, mutual positive affect and attachment security. Fifty-five grade five children and their mothers participated in a laboratory session comprised of various activities and completed questionnaires to evaluate attachment security. Joint planning and social problem solving were assessed observationally during an origami task. Problem solving effectiveness was unrelated to maternal teaching strategies, maternal encouragement and mutual positive affect. A marginally significant relationship was found between maternal encouragement and active child participation. Attachment security was found to be significantly related to sharing of responsibility during local planning, but only for child autonomous performance. An examination of conditional probabilities revealed that mutual positive affect did not increase the likelihood of subsequent mother-child dyadic regulation. However, mutual positive affect was found to be significantly related to both active child participation and dyadic regulation. The hypothesis predicting a mediational model was not supported. The implications of these findings in the theoretical and empirical literature were considered and suggestions for future research were made.

Collaborative reflection : supporting one practitioner's development of online learning communities /

This is a study of one participant's reflective practice as she worked to develop online communities in a face-to-face science course. Her process of reflective practice was examined in order to address factors that influenced her learning path, and the benefits and challenges of collaborative action research. These research goals were pursued using a collaborative action research methodology, initially chosen for its close match with Schon's (1983) model of reflective practice. The participant's learning fit vnth Mezirow's (1991) model of transformative learning. She began with beliefs that matched her goals, and she demonstrated significant learning in three areas. First, she demonstrated instrumental learning around the constraints of workload and time, and achieving online learning community indicators. Second, she demonstrated communicative learning that helped her to see her own needs for feedback and communication more clearly, and how other process partners had been a support to her. Third, her emancipatory learning saw her revisiting and questioning her goals. It was through the reflective conversation during the planned meetings and the researcher's reframing and interrogation of that reflection that the participant was able to clarify and extend her thinking, and in so doing, critically reflect on her practice as she worked to develop online learning communities. In this way, the collaborative action research methodology was an embodiment of co-constructivism through collaborative reflective practice. Schon's (1983) model of reflective practice positions a lone practitioners moving through cycles ofplan-act-observe-reflect. The results fi"om this study suggest that collaboration is an important piece of the reflective practice model.

Making it "click": collaborative perceptions of creative practice in art education /

Making it "Click": Collaborative Perceptions ofCreative Practice in Art Education examined the teaching practice of 6 art educators who conducted their work through the Niagara Falls Art Gallery's (NFAG) in-schools and Children's Museum programmes. These community resources service the elementary levels of participatory Public, Catholic and French schools in the Niagara Peninsula. The goal of this research was to find ways in which these teachers could explore their creative potential as art educators. The "click," a term introduced by participants indicating the coming together of all positive factors towards creativity, became the central theme behind this study. Research revealed that the effective creative process was not merely a singular phase, but rather a series of 4 processes: 1 , gathering knowledge; 2, intuitive and experiential; 3, the informal presentation of information in which creativity as a process was explored; and 4, formal presentation that took the analysis of information to a deeper, holistic level. To examine the ways in which experience and knowledge could be shared and brought together through a collaborative process, this study employed data collection that used literature research, interviews, focus group discussions, and personal journal entries. Follow-up discussions that assessed the effectiveness of action research, took place VA months after the initial meetings. It is hoped that this study might assist in creative educational practices, for myself as a member of the NFAG teaching team, for colleagues in the art programmes, art educators, and other teachers in the broader disciplines of education.

Engineering an improved adenovirus packaging cell line

Recombinant human adenovirus (Ad) vectors are being extensively explored for their use in gene therapy and recombinant vaccines. Ad vectors are attractive for many reasons, including the fact that (1) they are relatively safe, based on their use as live oral vaccines, (2) they can accept large transgene inserts, (3) they can infect dividing and postmitotic cells, and (4) they can be produced to high titers. However, there are also a number of major problems associated with Ad vectors, including transient foreign gene expression due to host cellular immune responses, problems with humoral immunity, and the creation of replication competent adenoviruses (RCA). Most Ad vectors contain deletions in the E1 region that allow for insertion of a transgene. However, the E1 gene products are required for replication and thus must be supplied in trans by a helper ceillille that will allow for the growth and packaging of the defective virus. For this purpose the 293 cell line (Graham et al., 1977) is used most often; however, homologous recombination between the vector and the cell line often results in the generation of RCA. The presence of RCA in batches of adenoviral vectors for clinical use is a safety risk because tlley . may result in the mobilization and spread of the replication-defective vector viruses, and in significant tissue damage and pathogenicity. The present research focused on the alteration of the 293 cell line such that RCA formation can be eliminated. The strategy to modify the 293 cells involved the removal of the first 380 bp of the adenovirus genome through the process of homologous recombination. The first step towards this goal involved identifying and cloning the left-end cellular-viral jUl1ction from 293 cells to assemble sequences required for homologous recombination. Polymerase chain reaction (PCR) was performed to clone the junction, and the clone was verified through sequencing. The plasn1id PAM2 was then constructed, which served as the targeting cassette used to modify the 293 cells. The cassette consisted of (1) the cellular-viral junction as the left-end region of homology, (2) the neo gene to use for positive selection upon tranfection into 293 cells, (3) the adenoviral genome from bp 380 to bp 3438 as the right-end region of homology, and (4) the HSV-tk gene to use for negative selection. The plasmid PAM2 was linearized to produce a double strand break outside the region of homology, and transfected into 293 cells using the calcium-phosphate technique. Cells were first selected for their resistance to the drug G418, and subsequently for their resistance to the drug Gancyclovir (GANC). From 17 transfections, 100 pools of G418f and GANCf cells were picked using cloning lings and expanded for screening. Genomic DNA was isolated from the pools and screened for the presence of the 380 bps using PCR. Ten of the most promising pools were diluted to single cells and expanded in order to isolate homogeneous cell lines. From these, an additional 100 G41Sf and GANef foci were screened. These preliminary screening results appear promising for the detection of the desired cell line. Future work would include further cloning and purification of the promising cell lines that have potentially undergone homologous recombination, in order to isolate a homogeneous cell line of interest.

Leadership and its impact on the success of Social Sciences and Humanities Research Council funded collaborative research projects

This dissertation investigates the practice of leadership in collaboratively designed and funded research in a university setting. More specifically, this research explores the meaning of leadership as experienced by researchers who were, or still are, engaged on Social Sciences and Humanities Research Council (SSHRC) funded collaborative research projects in a university setting. This qualitative study (Gay & Airasian, 2003) is situated within a social constructivist paradigm (Kezar, Carducci, & Contreras-McGavin, 2006) and involves an analysis of the responses from 12 researchers who answered 11questions related to my overarching research question: What is the impact of leadership on university based collaborative research projects funded by the Social Sciences and Humanities Research Council based on the experiences of researchers involved? The data that emerged supported and enhanced the existing literature related to leadership and collaborative groups in academia. The type of preferred leadership that emerged as a result of this research seemed to indicate that the type of leader that appeared to be optimal in this context might be described as a functional collaborative expert.

Introduction to engineering : a case study of an interdisciplinary course in Mathematics, Science and Technology

This thesis research was a qualitative case study of a single class of Interdisciplinary Studies: Introduction to Engineering taught in a secondary school. The study endeavoured to explore students' experiences in and perceptions of the course, and to investigate the viability of engineering as an interdisciplinary theme at the secondary school level. Data were collected in the form of student questionnaires, the researcher's observations and reflections, and artefacts representative of students' work. Data analysis was performed by coding textual data and classifying text segments into common themes. The themes that emerged from the data were aligned with facets of interdisciplinary study, including making connections, project-based learning, and student engagement and affective outcomes. The findings of the study showed that students were positive about their experiences in the course, and enjoyed its project-driven nature. Content from mathematics, physics, and technological design was easily integrated under the umbrella of engineering. Students felt that the opportunity to develop problem solving and teamwork skills were two of the most important aspects of the course and could be relevant not only for engineering, but for other disciplines or their day-to-day lives after secondary school. The study concluded that engineering education in secondary school can be a worthwhile experience for a variety of students and not just those intending postsecondary study in engineering. This has implications for the inclusion of engineering in the secondary school curriculum and can inform the practice of curriculum planners at the school, school board, and provincial levels. Suggested directions for further research include classroom-based action research in the areas of technological education, engineering education in secondary school, and interdisciplinary education.

Towards reverse engineering of Photosystem II: Synergistic Computational and Experimental Approaches

ABSTRACT Photosystem II (PSII) of oxygenic photosynthesis has the unique ability to photochemically oxidize water, extracting electrons from water to result in the evolution of oxygen gas while depositing these electrons to the rest of the photosynthetic machinery which in turn reduces CO2 to carbohydrate molecules acting as fuel for the cell. Unfortunately, native PSII is unstable and not suitable to be used in industrial applications. Consequently, there is a need to reverse-engineer the water oxidation photochemical reactions of PSII using solution-stable proteins. But what does it take to reverse-engineer PSII’s reactions? PSII has the pigment with the highest oxidation potential in nature known as P680. The high oxidation of P680 is in fact the driving force for water oxidation. P680 is made up of a chlorophyll a dimer embedded inside the relatively hydrophobic transmembrane environment of PSII. In this thesis, the electrostatic factors contributing to the high oxidation potential of P680 are described. PSII oxidizes water in a specialized metal cluster known as the Oxygen Evolving Complex (OEC). The pathways that water can take to enter the relatively hydrophobic region of PSII are described as well. A previous attempt to reverse engineer PSII’s reactions using the protein scaffold of E. coli’s Bacterioferritin (BFR) existed. The oxidation potential of the pigment used for the BFR ‘reaction centre’ was measured and the protein effects calculated in a similar fashion to how P680 potentials were calculated in PSII. The BFR-RC’s pigment oxidation potential was found to be 0.57 V, too low to oxidize water or tyrosine like PSII. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of iii tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. The results were used to develop a second generation of BFR-RC using a high oxidation pigment. The hypervalent phosphorous porphyrin forms a radical pair that can be observed using Transient Electron Paramagnetic Resonance (TR-EPR). Finally, the results from this thesis are discussed in light of the development of solar fuel producing systems.

Engineering school notebook which belonged to S.D. Woodruff

Engineering school notebook which belonged to S.D. Woodruff. This book contains logarithm notes, plane trigonometry, surveying and content of land. The outer page is torn and the notebook is quite discoloured. This does not affect the text. It has no covers, n.d.

Engineering school notebook which belonged to S.D. Woodruf

Engineering school notebook which belonged to S.D. Woodruff. This book contains questions for exercise as well as other mathematical topics. It also contains a page which has the title “The Cataract of Niagara in North America” and quite a few pages of repetitive lines as in “writing lines”. Some of the pages are loose or torn and the notebook is discoloured. This does not affect the text. This book has no covers, n.d.

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year, Dec. 1857.

Engineering services in marsh lands drainage for the months of October, November and December

Engineering services in marsh lands drainage for the months of October, November and December. This is signed by S.D. Woodruff, Dec. 31, 1856.