Radical translocation chemistry has classically been employed for the generation of carboncentred radicals as a means of remotely functionalising nominally unreactive sites. Previous work within the group had investigated vinyl radicals to effect translocation and had identified a need for a more reactive abstracting radical. In this regard, the high energy of alkoxyl radicals would facilitate rapid 1,5-hydrogen abstraction as opposed to simple reduction. This thesis describes the use of alkoxyl radicals, generated from N-alkoxyphthalimides, to abstract a hydrogen atom selectively from the α-position of a lactam ring. Alkoxyl radicals generated from precursors designed to lead to intramolecular trapping of the translocated radical were prone to β-scission in preference to 1,5-hydrogen atom abstraction. This is attributed to a combination of developing π-overlap in the transition state and stabilisation of the resulting radical both by nitrogen and the attached alkyl substituents. Incorporation of an alkenyl trap onto the lactam ring led to successful 1,5-hydrogen atom abstraction and stereoselective cyclisation, although β-scission remained the dominant pathway. Translocation initiated by nitrogen-centred radicals was investigated and it was found that 1,5-hydrogen abstraction occurred in preference to β-scission; intramolecular trapping of the translocated radical proved impossible either because the precursors were unstable to the reaction conditions or because increased steric bulk impeded hydrogen abstraction by the less reactive aminyl radical. Preparation of bicyclic pyrrolidinones via successive 5-endo-5-exo-trig cyclisations was investigated; the precursors were found to undergo direct reduction in preference to cyclisation. Alkyl or aryl groups attached to the a-acylamino carbon may lead to preferential 5-endo cyclisation by stabilisation of the developing radical in the transition state.

This thesis describes efforts to develop new methods for the synthesis of bridged azacycles using nitrogen-directed free radical rearrangements. Free radical addition to 7-azanorbornadienes were carried out to give 7-substituted 2- azanorbornenes (Scheme a.l, X-Y = RS-H or PhSe-H). [illustration in text ...] Scheme a. 1 Nitrogen-directed homoallylic radical rearrangement via intermolecular radical addition. A conceptually novel and theoretically interesting nitrogen-directed neophyl rearrangement (Scheme a.2) was developed into a synthesis of 2- azabenzonorbornanes 2. [illustration in text ...] Scheme a.2 Nitrogen-directed neophyl-like rearrangement to 2-azabenzonorbornanes. In this case the radical 1 was generated by Barton deoxygenation of 7- azabenzonorbornanols. The effect on rearrangement of bicyclic core substitution and of aromatic ring electronics was probed in some detail, and the process was synthetically useful for a wide range of substrates. Variation of the protecting group on nitrogen was investigated and the product profiles from neophyl-like rearrangement were consistent with a process driven by the stability of a radical α to nitrogen as a result of SOMO-lone pair orbital interaction. The kinetics and mechanism of these processes are examined where appropriate, leading to estimates of rate constants for the rearrangements.

This thesis analyses ideas of gender in the Swedish radical right. The aim of the study is to see if there are any differences or similarities in the way gender is being formulated by a populist radical right party as the Sweden Democrats (Sverigedemokraterna), the extreme right party, Party of the Swedes (Svenskarnas Parti) and the extreme right movement Swedish Resistance Movement (Svenska Motståndsrörelsen). Ideas of gender are presented in the theory chapter which is used later on in the analysis to compare with the radical right organisations of Sweden. To fulfil the aim we have performed a comparative ideological analysis between the three organisations and the base for our analysis is texts from each organisation’s webpage. The study shows that the ideological differences concerning gender between populism and extremism in the Swedish radical right are relatively small

A new portable flow tube technique, the Toronto Photo-Oxidation Tube v2.0 was developed and characterized to explore its potential to control and monitor the OH-initiated formation and chemical aging of secondary organic aerosol (SOA) in-situ. The first study investigated the different operational parameters of this flow tube technique. TPOT v2.0 can generate oxidizing conditions equivalent to ambient OH exposures of 2.3 – 10.8 days. The transmission efficiency of a model organic aerosol indicated negligible losses in the oxidation tube. Differences in the residence time distribution curves measured for a gas and model organic aerosol showed that particles were subjected to approximately half of the OH exposure compared to gases. The second study examined the capacity of the TPOT technique to generate secondary aerosols due to OH oxidation. High aerosol yield was observed for H2SO4 particles, whereas a low aerosol yield was observed for α-pinene SOA.

A new portable flow tube technique, the Toronto Photo-Oxidation Tube v2.0 was developed and characterized to explore its potential to control and monitor the OH-initiated formation and chemical aging of secondary organic aerosol (SOA) in-situ. The first study investigated the different operational parameters of this flow tube technique. TPOT v2.0 can generate oxidizing conditions equivalent to ambient OH exposures of 2.3 – 10.8 days. The transmission efficiency of a model organic aerosol indicated negligible losses in the oxidation tube. Differences in the residence time distribution curves measured for a gas and model organic aerosol showed that particles were subjected to approximately half of the OH exposure compared to gases. The second study examined the capacity of the TPOT technique to generate secondary aerosols due to OH oxidation. High aerosol yield was observed for H2SO4 particles, whereas a low aerosol yield was observed for α-pinene SOA.

The hydroxyl (OH) radical is a common intermediate species in any hydrogen- or hydrocarbon-based flame. Investigating OH at elevated temperatures and pressures is not a trivial task, and many considerations must be made to fully study the molecule. Shock tubes can provide the experimenter with a wide range of temperatures and pressures to investigate a variety of combustion characteristics including, but not limited to, OH kinetic profiles. Described in this dissertation is the diagnostic used to measure OH within a shock tube using UV absorption spectroscopy from an enhanced UV Xenon lamp passed through a spectrometer. OH absorption was made over a narrow range of wavelengths around 309.551 nm within the widely studied OH X→A ground vibrational transition region. Experiments have been performed in the shock-tube facility at Texas A&M University using this OH absorption diagnostic. A calibration mixture of stoichiometric H2/O2 diluted in 98% argon by volume was tested initially and compared with a well-known hydrogen-based kinetics mechanism to generate an absorption coefficient correlation. This correlation is valid over the range of conditions observed in the experiments at two pressures near 2 and 13 atm and temperatures from 1182 to 2017 K. Tests were completed using the absorption coefficient correlation on stoichiometric mixtures of methane, methane and water, ethane, ethylene, and acetylene to compare against a comprehensive, detailed chemical kinetics mechanism which considers up through C5 hydrocarbons. Measurements of methane show good agreement in peak OH formation and ignition delay time when compared with the mechanism. Improvements can be made in the shape of the methane-oxygen OH profile, and sensitivity and rate of production analyses were performed with the mechanism to identify key reactions for tuning. Similar results were found for methane-water-oxygen mixtures with no difference in profile shape or ignition delay time noted. There is room for improvement between the mechanism and measured values of OH for ethane-, ethylene-, and acetylene-based mixtures, although interesting pre-ignition features are nonetheless captured relatively well by the mechanism. Uncertainty in the measurement comes from the inherent noise in the photomultiplier tube signal and is ±25-150 ppm for the 2-atm experiments and ±6-25 ppm for the 13-atm experiments.

Radical polymerisation (RP) has for many years been an industrially important process, and the kinetics of the process remains an active area of research. As polymerisation proceeds, converting monomer (small molecules) into polymer (long chain molecules), chemical species of a variety of chain lengths are produced. Recent work has pointed toward the fact that rate coefficients for polymerisation reactions (specifically, termination and propagation) are often dependent on the chain-length of the reacting species. The focus of this thesis is to study the effects of chain-length-dependent reactions on the kinetics of RP, by using computer-based modeling and comparing the results of such modeling with experimental data. This enables the understanding of otherwise inexplicable trends and the building of more mechanistically detailed and accurate models for RP kinetics. In Chapter 2, a new model for termination is developed, connecting observations and analyses of termination kinetics at short chain lengths (particularly small molecule studies) with other observations and analyses at long chain lengths (conventional RP kinetics studies) in order to construct a model for termination that is shown to be capable of coherently describing termination kinetics at any chain length. In Chapter 3, this new model for termination is tested at short chain lengths on polymerisations with large quantities of added chain transfer agent. With the inclusion of chain-length-dependent propagation in the model, the model for termination is validated. Chapter 4 is aimed at extending an existing reduced-variable, compact, 'universal' description of steady-state RP kinetics by incorporating all known chain-length dependent reactivities. This both increases computational efficiency over other approaches and provides easily evaluated, approximate analytical expressions for RP kinetics. This foundational theory is applied in Chapter 5 to reach a deeper understanding of the behaviour of the model, and show how experimental data may readily be analysed to extract information about chain-length-dependent termination kinetics. In Chapter 6, the effect of chain-length dependent reactivities on the important technique of single-pulse pulsed-laser polymerisation is investigated, and this technique is validated as the best experimental method for investigation of termination kinetics. In general, a central result of this thesis is that chain-length-dependent reactivities, when acknowledged and properly incorporated into models, can explain many phenomena in RP kinetics which otherwise seem difficult to account for. No exceptions to this principle have been found.

Scramjet engines are the focus of considerable interest for propulsion in the hypersonic flow regime. One of the serious technical challenges for developing scramjets is reducing the skin friction drag on the engine. The combustion chamber, in particular, is a major contributor to the skin friction drag because of the high density of the flow through that region. This investigation focuses on reducing the combustion chamber skin friction drag by minimising the surface area and size of the combustion chamber and by employing a novel approach to accomplishing combustion. The first design criterion is addressed by using a single internal-combustor scramjet configuration, as opposed to multiple external combustors, and by injecting the fuel on the intake to reduce the mixing length required in the combustor. The second design criterion refers to the use of a new technique called radical farming. This uses the highly two-dimensional nature of the flow through the engine, which is created by deliberately ingesting the leading edge shocks, to achieve combustion at lower mean static pressures and temperatures than generally expected. A simplified approximate theoretical analysis of the radical farming concept is presented. Experiments were conducted in the T4 free-piston shock tunnel on a scramjet model with a single rectangular constant cross-sectional area combustion chamber. Pressure measurements were taken along the centreline of the intake, combustion chamber and thrust surface and across the model width at three locations. Gaseous hydrogen fuel was injected halfway along the intake at a range of equivalence ratios between zero and one. The combustion chamber height was varied from 20mm to 32mm, which varied the contraction ratio of the engine from 4.1 to 2.9. The experiments were conducted at a stagnation enthalpy of either 3MJ/kg or 4MJ/kg. The nominal 3MJ/kg condition corresponds to Mach 7.9 flight at an altitude of 24km. The majority of the 4MJ/kg experiments were conducted at a nominal condition corresponding to Mach 9.1 flight at an altitude of 32km. A small number of 4MJ/kg experiments were conducted at simulated flight altitudes of between 30 and 38km; the flight Mach number for these experiments was approximately 9.0. Thrust was calculated by integrating the centreline pressure distribution over the area of the thrust surface, assuming that the pressure at any axial location was constant across the engine width. These experimental thrust values were compared with theoretical estimates obtained using a one-dimensional analysis and a quasi-two-dimensional analysis. The comparison provided an indication of the level of completion of combustion in the experiments. The difference in thrust produced as a result of combusting fuel was examined by plotting the incremental specific impulse against equivalence ratio. Experimental and theoretical results agreed best at the higher equivalence ratios. Turbulent boundary layer separation correlations were used to provide reasonable estimates for the equivalence ratio at which the flow choked. The drag on the internal flowpath of the scramjet engine was estimated using the quasi-two-dimensional analysis. This drag estimate was combined with the experimental thrust measurements to provide estimates of the net specific impulse. Positive net specific impulse estimates were obtained above a certain minimum equivalence ratio, which depended on the contraction ratio and the test condition. The engine performance was observed to be highly dependent on the two-dimensional shock structure within the engine. Thrust and specific impulse were observed to decrease with increasing simulated flight altitude, as expected. Positive net specific impulse estimates were obtained at equivalence ratios of approximately one for simulated flight altitudes below 35km. Assuming complete combustion and that an equivalence ratio of one can be reached, the configuration considered in the present study can theoretically reach a net specific impulse of approximately 1000s at the 3MJ/kg condition and 500s at the 4MJ/kg condition. These numbers provide a promising testimonial for the use of this configuration, with modifications, as a more efficient alternative to rocket engines.

Thesis (Ph.D.) -- McMaster University, 2001. / Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1951. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves [80]-82).