Included in this file is a CD drive titled "Chapter Three: Supporting Information" with a 00:40 second long animation. For best quality, view in VLC, not Quicktime Player. / <p>Groundwater contamination by dense non-aqueous phase liquids (DNAPLs ), such as chlorinated solvents, continues to be a significant environmental problem. When released to the subsurface, either due to improper disposal or accidental release, DNAPLs can form complex source zones whose geometry is largely controlled by the geological heterogeneity of the subsurface. These source zones are composed of disconnected, immobile blobs or ganglia trapped by capillary forces (referred to as DNAPL residual) between high-saturation regions located at permeability interfaces (referred to as DNAPL pools). The slow dissolution of DNAPL pools can result in the contamination of groundwater for time periods on the order of decades to centuries.</p> <p>The common conceptual model used in the investigation of DNAPL-contaminated sites is based primarily on the mass transfer from DNAPL to the surrounding aqueous phase in the saturated zone. However, the presence of a discontinuous gas phase above a DNAPL pool can significantly affect the mass transfer from the pool through repeated, spontaneous expansion and mobilization of the gas phase. This mechanism has not been included in the common conceptual models.</p> <p>The goal of this research was to develop a quantitative understanding of discontinuous gas phase expansion and mobilization above a DNAPL pool. This goal was addressed using a combination of small-scale and intermediate-scale laboratory experiments. Small-scale, no-flow vial experiments were used to measure the expansion of single gas bubbles above DNAPL pools, and provide the basis for the development of an analytical model to assess the effect of expansion by multi-component partitioning on the mass transfer from DNAPL pools. Small-scale flow cell experiments were used to measure spontaneous expansion rates in porous media, and provide visual data concerning the distribution of the gas phase. Small-scale air injection experiments were used to characterize the gas flow. Finally, an intermediate-scale flow cell experiment was used to provide larger-scale data concerning the transient distribution of the gas phase, and measure the effect of spontaneous expansion and mobilization on the aqueous-phase DNAPL constituent concentrations.</p> <p>The combined results of these experiments established a detailed conceptual model for the spontaneous expansion and mobilization of a discontinuous gas phase above a DNAPL pool. In this conceptual model, spontaneous expansion of a discontinuous gas phase above a DNAPL pool occurs due to multi-component partitioning, and depends on the concentrations of both the volatile DNAPL and the other dissolved gases. This expansion is more likely to occur, and will be faster, in shallower systems (i.e. lower hydrostatic pressures) containing coarser media (i.e. lower capillary pressures), more volatile DNAPL, and higher concentrations of other dissolved gases (i.e. higher partial pressures). Mobilization of the expanding gas will occur as discontinuous gas flow in most sands, where the repeated trapping and coalescence of gas clusters can allow rapid, large-scale vertical transport of the gas phase. This discontinuous gas flow can produce macroscopic gas fingers composed of multiple, discrete gas clusters. These macroscopic fingers can reach substantial heights above the pool surface, but the growth occurs predominantly at the pool's leading edge due to the stripping of other dissolved gases. This expansion and mobilization can significantly affect the mass transfer from the DNAPL pool if the gas phase is in direct contact with the pool surface; or if the gas phase is close to the pool surface, covers a large fraction of the pool, and the groundwater flow is sufficiently slow. The partitioning of DNAPL constituent from the mobilized gas phase to the aqueous phase well above the pool surface can also change the spatial distribution of aqueous-phase DNAPL constituent concentrations, increasing them above those that are expected based on theoretical calculations for strictly DNAPL-water systems, even at elevations where the concentrations are expected to be zero. The increased concentrations well above the pool surface can appear as short-duration events in the presence of a sustained gas phase, due to the partitioning of DNAPL constituents from the gas to the aqueous phase during multi-component mass transfer. The results of this research provide the necessary basis to begin incorporating this fundamental mechanism into the conceptual and mathematical models used for DNAPL-related research, the investigation ofDNAPL-contaminated sites, and the design and application of DNAPL remediation technologies.</p> / Thesis / Doctor of Philosophy (PhD)

<p>The reduction of iron oxide from slag is involved in many processes, such as, bath smelting, EAF steelmaking and copper slag cleaning processes, and it is known to occur via gaseous intermediates. Four possible rate determining steps are involved during the reduction. Among them, these two interfacial chemical reactions, gas slag and gas carbon could ultimately limit the enhancement of these processes.</p><p>In this work, the gas slag reaction kinetics in slag cleaning of copper slags has been studied. The dissociation rate of CO2 on the surface of liquid copper slags is measured using an isotope exchange method, where the mass transfer in the gas phase was eliminated by using a sufficiently high gas flowrate.</p><p>It is found that, for slag of the FexO-SiO2-Al2O3-Cu2O system, the apparent rate constant remains fixed with Cu2O content from 1-10 wt pct at higher oxygen potentials. The rate constant becomes approximately 2 times higher after metallic copper is reduced from the slag, this is due to the suspension of small metal drops on the slag surface.</p><p>The effect of temperature in the range from 1200-1450°C on the rate constants was also studied. The activation energy was 190 kJ/mole for slag of composition 60FexO30SiO2-1 0Al2O3. In the presence of Cu metal~10%, the activation energy was reduced to 122 kJ/mole.</p> / Thesis / Master of Engineering (MEngr)

Hydrocarbons are an abundant resource of carbon and hydrogen. For example, fossil can be used to produce useful organic compounds. However hydrocarbons seem to be inert. Thus, the activation of the C-H bond is a popular research area. Metals play the main role in most catalysts that convert hydrocarbons to starting materials in industry. The study of metals is important because the properties of the metal core greatly influences the reactivity of a catalyst.1 The study of the chemistry of metals in the gas phase provides valuable information about the properties of metals. This information can be expanded to the chemistry of metals in the condensed phase. Furthermore, it is often both more accurate and more manageable to study the profile of a reaction in the gas phase than in the condensed phase.2,3 There are many studies about metal cations in the gas phase due to ease of their production. However metals have low electronegativity, limiting the study of gas phase metal anions. Recently, a simple and efficient method to generate atomic metal anions was developed at the University of Ottawa in Dr. Mayer's research laboratory.4-6 Atomic metal anions of Fe-, Co-, Cu-, Ag-, Cs- and K- were generated in an electrospray ionization (ESI) source of a mass spectrometer (MS). In this thesis study generated metal anions were reacted with small hydrocarbons of pentane, 1-pentene, 2-pentene and 1-pentyne to investigate the role of different metal anions in the activation of the C-H bond. Also metal anions were reacted with small alcohols of 1-butanol, 2-butanol and 2-methyl-2-propanol to compare the results. Metal anions showed a variety of reactions with these hydrocarbons and alcohols. Fe- was the only metal anion to show the electron transfer reaction, indicating that alcohols are more electronegative than Fe- and less electronegative than other metal anions. Fe-, Co- and Ag- showed the complex formation reaction. All metal anions showed the deprotonation reaction. A deprotonation reaction follows the harpoon mechanism, the long range proton abstraction7, and depends on the gas phase acidity of fragments. The most informative reaction observed was the dehydrogenation reaction because a metal-containing fragment is observed as a product in the spectrum of this reaction. The observation of a metal-containing fragment in the spectrum is significant because it emphasizes the important role that metal anions play in this reaction. This suggests that a dehydrogenation reaction involves metal insertion into a C-H bond. Among the transition metal anions, it was observed that Fe- and Cu- are more reactive than Co- and Ag- with regards to the dehydrogenation reaction, probably because Fe- and Cu- have a greater hydrogen affinity than Co- and Ag- that facilitates the hydrogen abstraction reaction. Another reason could be that Fe- and Cu- have a greater gas phase acidity that leads to a more stable intermediate in the course of the reaction. The results of this thesis study revealed that Cs- and K- could not abstract H from these substrates, probably due to the absence of occupied d orbitals that would facilitate insertion into a C-H bond. Some metal anions not only can insert into a C-H bond of alcohols but also can insert into a C-O bond of alcohols to form metal hydroxide anions. Alcohols are more reactive than hydrocarbons with regards to reactions with metal anions because they contain a functional group. This thesis study shows that some atomic metal anions are able to activate the C-H bond and abstract two hydrogens to form a double bond in hydrocarbons. It is probable that the electronic configuration, gas phase acidity and hydrogen affinity of the metal anions governs their reactivity.

Hydrocarbons are an abundant resource of carbon and hydrogen. For example, fossil can be used to produce useful organic compounds. However hydrocarbons seem to be inert. Thus, the activation of the C-H bond is a popular research area. Metals play the main role in most catalysts that convert hydrocarbons to starting materials in industry. The study of metals is important because the properties of the metal core greatly influences the reactivity of a catalyst.1 The study of the chemistry of metals in the gas phase provides valuable information about the properties of metals. This information can be expanded to the chemistry of metals in the condensed phase. Furthermore, it is often both more accurate and more manageable to study the profile of a reaction in the gas phase than in the condensed phase.2,3 There are many studies about metal cations in the gas phase due to ease of their production. However metals have low electronegativity, limiting the study of gas phase metal anions. Recently, a simple and efficient method to generate atomic metal anions was developed at the University of Ottawa in Dr. Mayer's research laboratory.4-6 Atomic metal anions of Fe-, Co-, Cu-, Ag-, Cs- and K- were generated in an electrospray ionization (ESI) source of a mass spectrometer (MS). In this thesis study generated metal anions were reacted with small hydrocarbons of pentane, 1-pentene, 2-pentene and 1-pentyne to investigate the role of different metal anions in the activation of the C-H bond. Also metal anions were reacted with small alcohols of 1-butanol, 2-butanol and 2-methyl-2-propanol to compare the results. Metal anions showed a variety of reactions with these hydrocarbons and alcohols. Fe- was the only metal anion to show the electron transfer reaction, indicating that alcohols are more electronegative than Fe- and less electronegative than other metal anions. Fe-, Co- and Ag- showed the complex formation reaction. All metal anions showed the deprotonation reaction. A deprotonation reaction follows the harpoon mechanism, the long range proton abstraction7, and depends on the gas phase acidity of fragments. The most informative reaction observed was the dehydrogenation reaction because a metal-containing fragment is observed as a product in the spectrum of this reaction. The observation of a metal-containing fragment in the spectrum is significant because it emphasizes the important role that metal anions play in this reaction. This suggests that a dehydrogenation reaction involves metal insertion into a C-H bond. Among the transition metal anions, it was observed that Fe- and Cu- are more reactive than Co- and Ag- with regards to the dehydrogenation reaction, probably because Fe- and Cu- have a greater hydrogen affinity than Co- and Ag- that facilitates the hydrogen abstraction reaction. Another reason could be that Fe- and Cu- have a greater gas phase acidity that leads to a more stable intermediate in the course of the reaction. The results of this thesis study revealed that Cs- and K- could not abstract H from these substrates, probably due to the absence of occupied d orbitals that would facilitate insertion into a C-H bond. Some metal anions not only can insert into a C-H bond of alcohols but also can insert into a C-O bond of alcohols to form metal hydroxide anions. Alcohols are more reactive than hydrocarbons with regards to reactions with metal anions because they contain a functional group. This thesis study shows that some atomic metal anions are able to activate the C-H bond and abstract two hydrogens to form a double bond in hydrocarbons. It is probable that the electronic configuration, gas phase acidity and hydrogen affinity of the metal anions governs their reactivity.

The research addresses two groups of reactions: chlorine atom reactions with fluorinated propenes and methyl amines. Most of the reactions were studied over a range of temperature and pressure with the goals of (i) assessing the potential importance of the reactions in atmospheric chemistry and (ii) obtaining kinetic and thermochemical information of fundamental physical–chemical interest. In the studies reported herein, laser flash photolysis (LFP) was coupled with time resolved atomic resonance fluorescence (RF) spectroscopic detection of chlorine atoms to investigate chlorine atom kinetics.

Gas-phase electron diffraction (GED) is the only viable technique for the accurate structural study of gas-phase molecules that contain more than ~10 atoms. Recent advances in Edinburgh have made it possible to study larger, more complex, stable molecules using the SARACEN method. This thesis is concerned with obtaining the structures of unstable species, using both standard GED techniques and by developing a new method in which ash vacuum pyrolysis is used to generate short-lived species in situ. In the first part of this thesis nine primary phosphines (R-PH2) with different substituents (R = methyl, vinyl, ethynyl, allenyl, allyl, propargyl, phenyl, benzyl and chloromethyl) are studied by GED. Vinylarsine and vinyldichloroarsine are also studied. Primary phosphines and arsines appear infrequently in the literature owing to their toxicity and high reactivity, especially of the unsaturated systems. The conformational behaviour in these molecules and trends throughout the series are rationalised. As appropriate, comparisons are made to analogous amines and the differences found are discussed. Tertiary phosphines (R3P) are routinely protected by complexation with borane (BH3) and it has been proposed that this technique could be extended to primary phosphines. As an extension of the initial investigation, the GED study of methylphosphine-borane offers an insight into structural changes that occur upon complexation, although attempts to study larger phosphine-borane complexes by GED proved dificult. The structures and bonding trends in a series of phosphineborane adducts are discussed, mainly using the results of ab initio calculations. The second part of the thesis details the implementation of a new, very high temperature nozzle, which allows the generation of short-lived species by pyrolysis. The workings of this nozzle are discussed and the study of the structure of ketene, generated from three different precursors, is detailed. The benzyl radical has also been studied, and a preliminary GED structure is presented. As a result of this work the molecular structures of Meldrum's acid and dibenzylsulfone are also presented, having been determined in the gas phase for the first time.

Optical spectroscopy combined with mass spectrometry provides a unique opportunity to probe the intrinsic properties of biologically-relevant ions in the gas phase, free from the interfering effects of solvent interactions in the condensed phase. Electrospray ionization allows large biomolecules to be transferred intact into the gas phase for mass analysis. Modern mass spectrometers provide excellent sensitivity, mass-resolution and can efficiently isolate a single ionic species from a complex mixture. However, the extent to which biomolecules retain their solution-phase conformations in the gas phase is largely unknown. Therefore, there is considerable interest in applying spectroscopic methods to biological ions in vacuuo. Due to the low number densities of ions in storage devices, traditional absorption measurements are not feasible, requiring more sensitive analytical methods. Two such techniques are laser-inducedfluorescence (LIF) and photo-dissociation (PD) action spectroscopy, both of which measure the consequence of absorption. The work in this dissertation describes applications of optical spectroscopic methods to interrogate mass-selected ions using a variety of ion storage apparatus including a Fourier transform ion cyclotron resonance mass spectrometer, a quadrupole ion trap and an electrostatic ion storage ring. First, the conformations of small cationized arginine complexes have been investigated using infrared multiple-photon dissociation (IRMPD) action spectroscopy in the IR fingerprint region of the spectrum (200-1800 cm-1). Second, an apparatus incorporating a quadrupole ion trap has been constructed in our laboratory to perform LIF and PD-action spectroscopy. The gas-phase fluorescence and photodissociation properties of three Rhodamine dyes have been investigated including fluorescence excitation and dispersed fluorescence spectra. Finally, the latter chapters describe the use of electronic action spectroscopy to investigate a model chromophore of the green fluorescent protein (GFP), p-hydroxybenzylidene-2,3-dimethylimidazolone (HBDI). The body of work in this dissertation highlights the integration of gas-phase spectroscopy and mass spectrometry to elucidate the fundamental photophysical properties of biological and related ions.

This study presents a detailed gas-phase and surface kinetic model for n-tetradecane autothermal reforming to deconvolute the complex reaction network that provides the mechanistic understanding of reforming chemistry in a packed-bed reactor. A thermodynamic analysis study for diesel reforming was performed to map the carbon formation boundary for various reforming processes. Through a Langmuir-Hinshelwood-Hougen-Watson (LHHW) type of kinetic model, which was derived using a simple mechanistic study, the need for a detailed kinetic study including both gas-phase reactions and surface reactions was identified. Pt-CGO (Pt on Gd doped CeO2) and Rh-pyrochlore catalysts were synthesized and characterized. In an accelerated test for reforming of commercial-diesel, Rh-pyrochlore catalyst showed stable performance for 24 hrs, whereas Pt-CGO catalyst deteriorated in 4 hrs. Minimum structural change in Rh-pyrochlore catalyst compared to Pt-CGO catalyst was observed using redox experiments. An experimental kinetic study with an inert silica bed provided clear evidence that the gas-phase reactions are important to the kinetics of hydrocarbon reforming. “Reaction Mechanism Generator” (RMG) software was employed to generate a detailed gas-phase kinetic model containing nine thousand three hundred and forty-seven elementary reactions and four hundred and fifty-nine species. The model was validated against n-tetradecane ignition delay data, and inert bed autothermal reforming data. The RMG model was also extended to capture the high pressure and low temperature pyrolysis chemistry to predict pyrolysis experimental data. The reactor simulation using the RMG model identified the detailed chemistry of the reactions in the pre-catalytic zone. Gas-phase oxidation/pyrolysis converts the heavier hydrocarbons and oxygen in the pre-catalytic zone to lower molecular weight products prior to reaching the catalyst surface. The steam reforming reactions that are dominant on the surface of the catalyst primarily involve lower molecular weight oxidation/pyrolysis products. A multi-component micro-kinetic model containing two hundred and seventy surface reactions and fifty-two adspecies was developed using a semi-empirical Unity Bond Index-Quadratic Exponential Potential (UBI-QEP) method. Transition State Theory estimates were used for elementary reactions up to C3 species, and simple fragmentation reactions were assumed for higher hydrocarbon species. Model simulations indicated on the catalyst surface that hydrogen is initially produced by the water-gas-shift reaction and subsequently by steam reforming reactions. A major reaction path for ethylene formation from 1,3 butadiene in the post-catalytic zone of the reactor was also identified. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2013-04-24 13:23:31.163

Gas phase studies of organometallic systems have provided deep insight into reaction mechanisms and reaction intermediates. In this thesis, several metal/ligand systems were examined in an effort to form metal carbenes in the gas phase. With cobalt and iron porphyrins, the carbene undergoes metal-ligand insertion. With copper bis-oxazolines, metal carbenes tend to undergo metal-ligand insertion and a Wolff rearrangement. To avoid insertions, we turned to a rigid ligand, 1, 10-phenanthroline. Under ESI conditions, a copper (I) complex with phenanthroline can be formed. When treated with diazoacetate esters, the dominant product results from addition with loss of nitrogen followed by loss of CO. This appears to be the result of a Wolff rearrangement of the metal carbene to give a metal ketene complex that spontaneously loses CO. There is no evidence of any stable metal carbenes in this reaction system. Trimethylsilyldiazomethane was also used as a carbene precursor, and its reaction with the copper phenanthroline complex gives addition with loss of nitrogen; but the product exhibits no carbene reactivity with alkenes. Here computational modeling suggests that the metal carbene undergoes a 1, 2 methyl migration, giving an exceptionally stable sila-alkene complex with the copper. As an alternative path to a metal carbene, we have used ESI to form a complex between the copper (I) phenanthroline and betaine (N, N, N-trimethylglycine). Under CID, this complex wills decarboxylates to give a copper ylide complex. Further CID leads to loss of trimethylamine and the formation of a complex between methylene and the copper phenanthroline. Depending on the CID conditions, two isobaric products are formed. One exhibits no carbene reactivity and the other readily gives carbene behavior with alkenes. The former is likely a metal-ligand insertion product, and the latter is the true metal carbene species. We explored the reactions of the carbene with electron-rich alkenes, such as ethyl vinyl ether and 3, 4-dihydro-2H-pyran, and electron-deficient alkenes, such as trichloroethylene.

The role of the solvent in ionic and ion-molecule interactions is of fundamental importance in kinetics and thermodynamics of solution chemistry. However, the study of the ionic interactions in the presence of a large number of solvent molecules is very challenging. Therefore, the gas-phase is the appropriate medium to study such reactions on a molecular level where the ion-solvent interaction can be examined by studying ions surrounded with a cluster of solvent molecules in the complete absence of the any interference caused by the bulk of the solvent. In nature, organic ions can form hydrogen bonds with solvents. An insight into basic molecular interactions is required to be extracted from the gas phase energies and structures of the solvated organic ions. Therefore, the stepwise hydration experiments of benzene.+, C3H3+, acetylene.+, pyridine.+, 2-fluoropyridine.+, phenyl acetylene.+ and acetylene dimer.+ have been investigated using quadrupole mass-selected ion mobility mass spectrometer. Thus, these systems can be considered as prototypical models for understanding the molecular aspects leading to hydrophobic hydration in the condensed phase. Two routes of the investigation of ion-molecule interactions are considered in this dissertation. The first route is concerned with injecting the same ion into various solvents to study the nature and strength of the ion-solvent interactions when protonated pyrimidine cation interacts with water, methanol and acetonitrile molecules. Association and proton transfer reactions were observed. On the other hand, the second route involves the injection of various ions into the same solvent where the interactions of hydrogen cyanide (HCN) molecules with different ions. Benzene, phenyl acetylene, pyridine, protonated pyridine, and pyrimidine ions were investigated. All the investigated ions exhibited hydrogen bonding with the hydrogen cyanide molecules with variable strength depending on the charge distribution on the specified ion as well as the nature of interaction. Additionally, ion mobility structural methods were utilized to investigate structures of binary clusters formed by supersonic expansion of mixed vapors. The structures can be identified by comparing the experimentally measured collision cross section values with those predicted from DFT computations.