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Spontaneous expansion and mobilization of a discontinuous gas phase due to mass transfer from dense non-aqueous phase liquid / SPONTANEOUS EXPANSION AND MOBILIZATION OF GAS ABOVE DNAPLMumford, Kevin G. 10 1900 (has links)
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)
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Gas Slag Reaction Kinetics in Slag Cleaning of Copper SlagsChen, Elaine (Xiao Ming) 01 1900 (has links)
<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)
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<b>GAS-PHASE ION-ION CHEMISTRY FOR LIPID STRUCTURAL CHARACTERIZATION AND FOR REACTIONS IN A MOLECULAR CONTAINER</b>Sarah Twumwah Nsiah (19183795) 21 July 2024 (has links)
<p dir="ltr">This thesis focuses on ion-ion reactions for making ions for lipid structural elucidation and chemical reactions.</p>
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Catalytic co-valorization of C1 and N1 compounds towards nitrile chemicalsMartínez Monje, María Elena 04 July 2025 (has links)
[ES] El panorama industrial actual se enfrenta a desafíos significativos mientras transita hacia la descarbonización y la sostenibilidad, impulsado por el imperativo de lograr emisiones netas cero para 2050. Se espera una importante contribución hacia este objetivo al conectar materias primas no convencionales y renovables, alternativas a los materiales fósiles convencionales como el petróleo, a las cadenas de valor existentes de la industria química.
Actualmente, existe un creciente interés industrial en la producción de nitrilos de cadena corta como HCN y acetonitrilo, mientras que se espera que las tasas de demanda global disminuyan en los próximos años en el caso del acrilonitrilo. Como reemplazo para materias primas convencionales para la producción de nitrilos, como las olefinas ligeras C2-3 de origen fósil, el desarrollo de rutas de conversión selectivas a partir de bloques de construcción C1 renovables, como el bio/e-syngas o su derivado metanol, y precursores N1 renovables, como el amoníaco verde, proporciona rutas hacia los productos químicos nitrilos, prospectivamente con una huella de carbono más baja.
La presente tesis desarrolla y estudia catalizadores sólidos capaces de dirigir simultáneamente reacciones de acoplamiento C-N y C-C para la producción de nitrilos alifáticos C2+, particularmente acetonitrilo. Se hace hincapié en desvelar la naturaleza y estructura del verdadero catalizador activo, que se desarrolla bajo las condiciones del proceso. Específicamente, la tesis estudia efectos promocionales provocados por la combinación de dos metales en compuestos intersticiales mixtos de metales, aleaciones y compuestos intermetálicos.
En primer lugar, se realizan estudios catalíticos y teóricos complementarios de Teoría del Funcional de la Densidad (DFT) sobre la conversión de mezclas de amoníaco (N1) y gas de síntesis (C1, CO+H2) a acetonitrilo con un (pre)catalizador monometálico MoO3. Estos estudios demuestran que MoN1-x, que se desarrolla mediante nitridación superficial, es el catalizador activo real y sugieren que la activación disociativa de HCN, asistida por oxígeno, es el paso controlante de la cinética de formación de acetonitrilo.
A continuación, se estudian efectos promocionales de metales de transición divalentes de primera fila en catalizadores basados en molibdeno, utilizando un conjunto de compuestos de molibdato mixto cristalino, estructuralmente análogos, como precursores de catalizador. El dopado con Mn (Mn:Mo ~1) proporciona un catalizador particularmente selectivo y estable para la síntesis de acetonitrilo a partir de mezclas de NH3/gas de síntesis, logrando una tasa de formación de acetonitrilo de 50·10-3 mmol gcat-1 min-1 a 723K. Un conjunto de métodos in situ y operando con sensibilidad bulk y superficial, proporcionan evidencias de que un oxinitruro mixto MnM, con una simetría Fm-3m, y rico en defectos estructurales, representa el catalizador activo. Se sugiere que la mayor oxofilia del oxinitruro mixto MnMo, junto con el papel clave del oxígeno superficial para la activación disociativa de HCN, subyacen al efecto sinérgico de ambos metales.
Finalmente, se estudió la conversión de mezclas en fase vapor de metanol (C1) y amoníaco (N1) a compuestos nitrogenados sobre nanocristales bimetálicos GaNi soportados en SiO2. Las aleaciones desordenadas de GaNi (Ga/(Ga+Ni)< 20%) son particularmente selectivas hacia la síntesis de nitrilos, mientras que los compuestos intermetálicos GaNi (Ga/(Ga+Ni)> 40%) catalizan principalmente la aminación de metanol a metilaminas. La difracción de rayos X y espectroscopía de absorción de rayos X, in situ y operando, revelan que el galio es un promotor necesario, el cual contribuye a la estabilización de fases expandidas de fcc Ni(C,N) así como Ni3C, a temperaturas relevantes para la catálisis (673-773K), cuyo desarrollo en la superficie del catalizador corresponde al inicio de la producción de nitrilos C2+ mediante la integración de reacciones de acoplamiento C-N y C-C. / [CA] El panorama industrial actual s'enfronta a desafiaments significatius mentres transita cap a la descarbonització i la sostenibilitat, impulsat per l'imperatiu d'aconseguir emissions netes zero per a 2050. S'espera una important contribució cap a este objectiu en connectar matèries primeres no convencionals i renovables, alternatives als materials fòssils convencionals com el petroli, a les cadenes de valor existents de la indústria química.
Actualment, existix un creixent interés industrial en la producció de nitrils de cadena curta com HCN i acetonitril, mentres que s'espera que les taxes de demanda global disminuïsquen en els pròxims anys en el cas del acrilonitrilo. Com a reemplaçament per a matèries primeres convencionals per a la producció de nitrils, com les olefines lleugeres C2-3 d'origen fòssil, el desenvolupament de rutes de conversió selectives a partir de blocs de construcció C1 renovables, com el bio/e-syngas o el seu derivat metanol, i precursors N1 renovables, com l'amoníac verd, proporciona rutes cap als productes químics nitrils, prospectivament amb una petjada de carboni més baixa.
La present tesi desenvolupa i estudia catalitzadors sòlids capaços de dirigir simultàniament reaccions d'acoblament C-N i C-C per a la producció de nitrils alifàtics C2+, particularment acetonitril. Es posa l'accent a revelar la naturalesa i estructura del verdader catalitzador actiu, que es desenvolupa sota les condicions del procés. Específicament, la tesi estudia efectes promocionals provocats per la combinació de dos metalls en compostos intersticials mixtos de metalls, aliatges i compostos intermetàl·lics.
En primer lloc, es realitzen estudis catalítics i teòrics complementaris de Teoria del Funcional de la Densitat (DFT) sobre la conversió de mescles d'amoníac (N1) i gas de síntesi (C1, CO + H2) a acetonitril amb un (pre)catalitzador monometálico MoO3. Estos estudis demostren que MoN1-x, que es desenvolupa mitjançant nitridació superficial, és el catalitzador actiu real i suggerixen que l'activació dissociativa de HCN, assistida per oxigen, és el pas controlante de la cinètica de formació d'acetonitril.
A continuació, s'estudien efectes promocionals de metalls de transició divalentes de primera fila en catalitzadors basats en molibdé, utilitzant un conjunt de compostos de molibdat mixt cristal·lí, estructuralment anàlegs, com a precursors de catalitzador. El dopat amb Mn (Mn:Mo ~1) proporciona un catalitzador particularment selectiu i estable per a la síntesi d'acetonitril a partir de mescles de NH3/gas de síntesi, aconseguint una taxa de formació d'acetonitril de 50·10-3 mmol gcat-1 min-1 a 723 K. Un conjunt de mètodes in situ i operant amb sensibilitat bulk i superficial, proporcionen evidències que un oxinitrur mixt MnM, amb una simetria Fm-3m, i ric en defectes estructurals, representa el catalitzador actiu. Se suggerix que la major oxofilia del oxinitrur mixt MnMo, juntament amb el paper clau de l'oxigen superficial per a l'activació dissociativa de HCN, subjauen a este efecte sinèrgic de tots dos metalls.
Finalment, es va estudiar la conversió de mescles en fase vapor de metanol (C1) i amoníac (N1) a compostos nitrogenats sobre nanocristalls bimetàl·lics GaNi suportats en SiO2. Els aliatges desordenats de GaNi (Ga/(Ga+Ni)< 20 %) són particularment selectives cap a la síntesi de nitrils, mentres que els compostos intermetàl·lics GaNi (Ga/(Ga+Ni)> 40 %) catalitzen principalment l'aminació de metanol a metilamines. La difracció de raigs X i espectroscòpia d'absorció de raigs X, in situ i operant, revelen que el gal·li és un promotor necessari, el qual contribuïx a l'estabilització de fases expandides de fcc Ni(C,N) així com Ni3C, a temperatures rellevants per a la catàlisi (673-773 K), el desenvolupament de la qual en la superfície del catalitzador correspon a l'inici de la producció de nitrils C2+ mitjançant la integració de reaccions d'acoblament C-N i C-C. / [EN] The current industrial landscape is facing significant challenges as it transitions towards decarbonization and sustainability, driven by the imperative of achieving net-zero emissions by 2050. An important contribution towards this goal is expected from connecting unconventional and renewable feedstocks, alternative to conventional fossil raw materials such as crude oil, to existing value chains of the chemical industry.
There is currently growing industrial interest in the production of short-chain nitriles such as acid cyanide and acetonitrile, while lower global demand rates are expected in the next years for acrylonitrile. Departing from conventional raw materials for nitrile production, such as C2-3 light olefin petrochemicals, the development of selective conversion routes from renewable C1 building blocks, such as bio/e-syngas or its derivative methanol, and renewable N1 precursors, like green ammonia, provides prospectively lower carbon footprint routes towards nitrile commodity chemicals.
The present thesis develops and studies solid catalysts able to concomitantly steer C-N and C-C coupling reactions for the production of C2+ aliphatic nitrile N-chemicals, precisely acetonitrile. Emphasis is placed on unveiling the nature and structure or the true working catalyst, which develops under relevant process conditions. Specifically, the thesis studies promotional effects brought about by the combination of two metals in mixed-metal interstitial compounds, alloys and intermetallic compounds.
First, complementary catalytic and theoretical Density Functional Theory studies on the conversion of mixtures of ammonia (N1) and syngas (C1, CO and H2) to acetonitrile with a monometallic MoO3 (pre)catalyst show MoN1-x, which develops upon near-surface nitridation, as the actual working catalyst and suggest O-assisted dissociative activation of HCN as a kinetically controlling step towards acetonitrile and higher nitriles.
Next, promotional effects by first-row divalent transition metals on molybdenum-based catalysts are studied, using a set of structurally analogous crystalline ammonium mixed-metal molybdate compounds as catalyst precursors. Doping with Mn (Mn:Mo ~1) affords a particularly selective and stable catalyst for acetonitrile synthesis from NH3/syngas mixtures, achieving an acetonitrile formation rate of 50·10-3 mmol gcat-1 min-1 at 723 K. A battery of in situ and operando bulk and near-surface sensitive methods provide evidence that a defective MnMo mixed-metal oxynitride, with a Fm-3m symmetry, best represents the working catalyst. The higher oxophilicity of the mixed-metal MnMo oxynitride, alongside the key role of surface oxygen for HCN dissociative activation, is suggested to underlie the Mn-Mo bimetallic synergistic effect.
Finally, the conversion of vapor mixtures of methanol (C1) and ammonia (N1) to N-compounds was studied on SiO2-supported GaNi bimetallic nanocrystals. Disordered GaNi alloys (Ga/(Ga+Ni)< 20 %) show to be particularly selective towards nitrile synthesis, whereas GaNi intermetallic compounds (Ga/(Ga+Ni)> 40 %) catalyzed primarily methanol amination to methylamines. In situ and operando X-ray diffraction and X-ray absorption spectroscopy reveal that Ga is a necessary promoter in nickel-based nanocrystals, contributing to the stabilization of expanded fcc Ni(C,N) and Ni3C phases at catalysis relevant temperatures (673-773 K), whose development on the catalyst surface corresponds to the onset of C2+ nitrile production by integration of C-N and C-C coupling reactions. / Martínez Monje, ME. (2024). Catalytic co-valorization of C1 and N1 compounds towards nitrile chemicals [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/207107
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The Investigation of Reactions of Atomic Metal Anions with Small Hydrocarbons and Alcohols in the Gas PhaseHalvachizadeh, Jaleh 21 February 2014 (has links)
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.
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The Investigation of Reactions of Atomic Metal Anions with Small Hydrocarbons and Alcohols in the Gas PhaseHalvachizadeh, Jaleh January 2014 (has links)
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.
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Laser flash photolysis studies of chlorine atom reactions with fluorinated propenes and methyl aminesMazumder, Shrila 27 August 2014 (has links)
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.
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Gas-phase electron diffraction studies of unstable moleculesNoble-Eddy, Robert January 2009 (has links)
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.
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Optical Spectroscopy of Mass-selected Ions in the Gas PhaseForbes, Matthew William 12 August 2010 (has links)
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.
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A COMBINED GAS-PHASE AND SURFACE REACTION MECHANISTIC MODEL OF DIESEL SURROGATE REFORMING FOR SOFC APPLICATIONPARMAR, RAJESH 24 April 2013 (has links)
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
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