Dissertations / Theses on the topic 'Detailed chemical kinetic mechanism'
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Davidson, Jeffrey E. "Combustion Modeling of RDX, HMX and GAP with Detailed Kinetics." BYU ScholarsArchive, 1996. https://scholarsarchive.byu.edu/etd/6531.
Shaheen, Zeiwar Hussein [Verfasser], Bernd [Akademischer Betreuer] Rogg, and Viktor [Akademischer Betreuer] Scherer. "Development of detailed and reduced bio-diesel kinetic chemical mechanisms / Zeiwar Hussein Shaheen. Gutachter: Bernd Rogg ; Viktor Scherer." Bochum : Ruhr-Universität Bochum, 2016. http://d-nb.info/1082425818/34.
Dmitriev, Artëm. "Kinetic study of ester biofuels in flames." Electronic Thesis or Diss., Université de Lorraine, 2020. http://www.theses.fr/2020LORR0238.
Global progress all over the world requires a variety of clean energy sources. Liquid ester-based biofuels seem to be very effective in this context since they are easy to use in modern vehicles, they can be produced from a variety of renewable resources, and they provide environmentally friendly combustion characteristics. In this regard, fatty acid ethyl esters (FAEEs) are considered as a promising class of biofuels. The main goal of this thesis was to develop an updated chemical kinetic mechanism of combustion of light FAEEs up to ethyl pentanoate and validate it against the new experimental data on chemical speciation in low and atmospheric pressure premixed laminar flames. The flames fueled by three FAEEs, ethyl acetate, ethyl butanoate and ethyl pentanoate, were investigated by means of molecular-beam mass-spectrometry and gas-chromatography. More than 40 stable and intermediate species including radicals were detected and quantified in the flames. A comprehensive analysis of the developed mechanism was performed. The thesis consists of 3 chapters. In the first chapter a review of literature is presented. The most important experimental and theoretic studies on FAEEs are discussed. The second chapter presents an overview of experimental and simulation methods used in the work. Details on the mechanism development are also provided in this part. The last chapter present experimental and modeling results on the esters studied in comparison with the literature kinetic mechanisms
Maurice, Lourdes Quintana. "Detailed chemical kinetic models for aviation fuels." Thesis, Imperial College London, 1996. http://hdl.handle.net/10044/1/8153.
Potter, Mark Lee. "Detailed chemical kinetic modelling of propulsion fuels." Thesis, Imperial College London, 2004. http://hdl.handle.net/10044/1/7995.
Rizos, Konstantinos-Athanassios. "Detailed chemical kinetic modelling of homogeneous systems." Thesis, Imperial College London, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.407143.
Park, Sung-Woo. "Detailed chemical kinetic model for oxygenated fuels." Thesis, Imperial College London, 2012. http://hdl.handle.net/10044/1/9599.
Pacheco, Augusto Finger. "Analysis and reduction of detailed chemical kinetics mechanisms for combustion of ethanol and air." reponame:Repositório Institucional da UFSC, 2016. https://repositorio.ufsc.br/xmlui/handle/123456789/172793.
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Neste trabalho, três mecanismos detalhados de cinética química para o etanol, disponíveis na literatura, foram submetidos a diferentes métodos de redução, utilizando condições encontradas na operação normal de motores de combustão interna como parâmetros de redução. O primeiro mecanismo selecionado foi desenvolvido por Leplat e colaboradores (2011), no ICARE, em Orleans, França, contendo 252 reações químicas reversíveis, compreendendo 38 espécies, obtido principalmente para reproduzir medidas de concentrações de espécies em reatores perfeitamente misturados. O segundo por Mittal e colaboradores (2014), no C3-NUI, na Irlanda, envolvendo 710 reações químicas reversíveis, englobando 111 espécies, desenvolvido para prever os atrasos de ignição medidos em máquinas de compressão rápida. O terceiro mecanismo selecionado foi produzido por Cancino e colaboradores (2010), do IVG, Alemanha, e da UFSC, Brasil, contendo 1349 reações químicas reversíveis, compreendendo 35 espécies, feito principalmente para prever atrasos de ignição à alta pressão em tubos de choque. Os métodos de redução selecionados foram: Sensitivity Analysis (SA), Rate of Production (ROP), Direct Relation Graph (DRG), Direct Relation Graph with Error Propagation (DRGEP) e Path Flux Analysis (PFA). Sendo o mecanismo do Leplat o mais compacto, este foi utilizado para avaliar a redução final e a razão de convergência de cada método estudado. Ambos, atrasos de ignição (Ignition Delay Times, IDT) e velocidade de chama laminar, compreendidos em um grande intervalo de condições de temperatura, pressão e razão de equivalência foram selecionados como parâmetros de redução. Da análise inicial, os métodos DRG e DRGEP apresentaram as maiores eficiências, tanto em termos de tamanho final do mecanismo reduzido como nos termos de taxa de remoção de espécies. Assim, ambos os métodos foram sistematicamente aplicados nos outros mecanismos e as diferenças entre as espécies removidas foram avaliadas. O mecanismo final obtido via DRGEP para o mecanismo do Leplat apresentou, respectivamente, 84% e 72% das espécies e reações do mecanismo detalhado. Para o mecanismo do Cancino, o DRGEP apresentou uma maior redução, com 58% e 61% respectivamente das espécies e reações sem remover o mecanismo de oxidação do nitrogênio e ainda representando o IDT à altas pressões com uma diferença menor de 5% do mecanismo detalhado. Finalmente, para o mecanismo do Mittal, o método DRG apresentou a maior redução, atingindo 37% das espécies e 34% das reações do mecanismo detalhado. A análise de sensibilidade dos mecanismos reduzidos revelaram o mesmo grupo de reações como as mais sensíveis para a chama laminar e IDT dos apresentados pelos mecanismos detalhados, indicando que a redução não modifica a razão de importância das reações dentro de um caminho de reação para um dado mecanismo. Entretanto, ao comparar os mecanismos reduzidos entre si, muitas diferenças se tornam visíveis, como a modelagem dos fenômenos inicias ou finais da combustão. Estas observações podem auxiliar e dirigir o desenvolvimento de mecanismos cinéticos mais abrangentes para a modelagem da combustão de etanol.
Abstract : In this work, three detailed kinetic mechanisms available in the literature were subjected to different methods of reduction, using the conditions found on internal combustion engines normal operation as reduction targets. The mechanisms selected were those of Leplat and co-workers (2011), from ICARE, Orleans, France, containing 252 reversible chemical reactions among 38 chemical species, developed mainly to reproduce measurements of species concentration in perfectly-stirred reactors; of Mittal and co-workers (2014), from C3-NUI, Ireland, involving 710 reversible chemical reactions among 111 chemical species, developed mainly to predict ignition delay time measured in rapid compression machine; and that of Cancino and co-workers (2010), from IVG, Germany, and UFSC, Brazil, involving 1349 reversible chemical reactions among 135 chemical species, mainly developed to predict high-pressure ignition delay time measured in shock tubes. The reduction methods selected were the Sensitivity Analysis (SA), Rate of Production (ROP), Directed Relation Graph (DRG) and Directed Relation Graph with Error Propagation (DRGEP) and Path Flux Analysis (PFA). Since Leplat's mechanism is the most compact, it was selected for the assessment of the final reduction and convergence ratio involved in each reduction method studied. Both ignition delay time and laminar flame speed, evaluated over a large range of temperature, pressure and equivalence ratios, were selected as reduction targets. The maximum difference allowed between the predictions of the full detailed and the reduced mechanisms was 5 % over the entire target range. From the initial analysis, the DRG and DRGEP methods appeared as the most effective, both in terms of the size of the final reduced mechanism, as well as in terms of the rate of removal of species. The DRG and DRGEP methods were then systematically applied to the other mechanisms and the differences observed in the reduced species were noted and analyzed. The final reduced mechanism obtained via DRGEP from Leplat´s mechanism presented, respectively, 84 % and 72 % of the species and reactions of the detailed mechanism. For the Cancino mechanism, the DRGEP produced a larger reduction with 58 % and 61 % of species and reactions respectively of the detailed mechanism, without removing the nitrogen oxidation mechanism and still representing the high-pressure IDT with a 5% difference from the detailed mechanism. Finally, for the Mittal mechanism, the DRG method presented the largest reduction, reaching 37% of species and 34% of reactions of the detailed mechanism. The sensitivity analysis of the reduced mechanisms revealed the same group of most sensitive reactions in respect to the laminar flame and ignition delay time as the detailed mechanism, indicating that the reduction does not change the relative importance of the reactions within a reaction path for a given mechanism. However, when the reduced mechanisms are compared among them, several basic differences arise, mainly in the level of detail, expressed as the number of intermediates and reactions, placed in modeling early or late kinetics phenomena. These observations may lead to the development of more comprehensive mechanisms for the modeling of ethanol combustion.
Porter, Richard Thomas James. "Kinetic mechanism reduction for chemical process hazard application." Thesis, University of Leeds, 2007. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.441227.
Cho, Yong Kweon. "Kinetic and Chemical Mechanism of Pyrophosphate-Dependent Phosphofructokinase." Thesis, University of North Texas, 1988. https://digital.library.unt.edu/ark:/67531/metadc332128/.
Tripathi, Rupali [Verfasser]. "Detailed Chemical Kinetic Modeling of Biofuels and their Blends with Conventional Fuel Components / Rupali Tripathi." Düren : Shaker, 2020. http://d-nb.info/1213471850/34.
Berdis, Anthony J. (Anthony Joseph). "Kinetic and Chemical Mechanism of 6-phosphogluconate Dehydrogenase from Candida Utilis." Thesis, University of North Texas, 1993. https://digital.library.unt.edu/ark:/67531/metadc278323/.
Bakhtina, Marina M. "Application of chemical probes to study the kinetic mechanism of DNA polymerases." Columbus, Ohio : Ohio State University, 2006. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=osu1148915981.
Jiang, Mofen. "The Chemical and kinetic mechanism for leaching of chrysocolla by sulfuric acid." Thesis, The University of Arizona, 1992. http://etd.library.arizona.edu/etd/GetFileServlet?file=file:///data1/pdf/etd/azu_e9791_1992_610_sip1_w.pdf&type=application/pdf.
Tai, Chia-Hui. "Kinetic and Chemical Mechanism of O-Acetylserine Sulfhydrylase-B from Salmonella Typhimurium." Thesis, University of North Texas, 1993. https://digital.library.unt.edu/ark:/67531/metadc279064/.
KONOPKA, THIAGO FABRICIUS. "COMPARATIVE STUDY OF DETAILED CHEMICAL KINETIC MODELS OF SOOT PRECURSORS FOR ETHYLENE/AIR AND METHANE/AIR COMBUSTION." PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO, 2014. http://www.maxwell.vrac.puc-rio.br/Busca_etds.php?strSecao=resultado&nrSeq=23399@1.
Essa dissertação apresenta um estudo comparativo de quatro diferentes modelos de cinética química detalhada que envolvem as principais espécies químicas responsáveis pelo processo de formação e oxidação da fuligem, i.e., o oxigênio molecular, o radical hidroxila, o acetileno, o propargil, benzeno, fenil e pireno. Para este fim, considera-se a combustão de misturas de etileno/ar e metao/ar. Para analisar os modelos cinéticos são utilizados um reator perfeitamente misturado (PSR) e um reator parcialmente misturado (PaSR). No caso do reator perfeitamente misturado, um estudo sistemático da influência do tempo de residência e a riqueza da mistura sobre estas espécies químicas é apresentado. São discutidas as importantes discrepâncias obtidas, para o acetileno, o propargil, o benzeno, o fenil e o pireno, entre os modelos cinéticos analisados. As espécies oxidantes exibem menores discrepâncias dentre todas as espécies analisadas. No caso do reator parcialmente misturado, a razão entre o tempo de residência e o tempo de mistura é o parâmetro de análise. De modo geral, os resultados obtidos permitem avaliar o comportamento dos mecanismos cinéticos em uma situação representativa de combustão em escoamentos turbulentos.
In this dissertation a comparative study is presented of four different detailed kinetics models involving the main chemical species responsible for the soot formation and oxidation, i.e., the molecular oxygen, the hydroxyl, the acetylene, the propargyl, the benzene and the pyrene. To this purpose is considered the combustion of ethylene/air and metane/air. To analyze the kinetic models are used a perfect stirred reactor (PSR) and a partial stirred reactor (PaSR). In the case of a perfect stirred reactor a systematic study of the influence of the residence time and of the equivalence ratio on these chemical species is presented. Are discussed the important discrepancies obtained for acetylene, propargyl, benzene, phenyl and pyrene, between the kinetic models analyzed. The oxidizing species exhibit minor discrepancies only. In the case of the partially mixed reactor, the ratio between the residence time and the mixing time is the analysis parameter. Overall, the results obtained allow to evaluate the behavior of the kinetic mechanisms in situations representative of combustion in turbulent flows.
Cai, Liming [Verfasser]. "Chemical Kinetic Mechanism Development and Optimization for Conventional and Alternative Fuels / Liming Cai." Aachen : Shaker, 2016. http://d-nb.info/1118259327/34.
Frantom, Patrick Allen. "Studies of the chemical and regulatory mechanisms of tyrosine hydroxylase." Texas A&M University, 2006. http://hdl.handle.net/1969.1/3817.
Matheu, David M. (David Michael) 1974. "Integrated pressure-dependence in automated mechanism generation : a new tool for building gas-phase kinetic models." Thesis, Massachusetts Institute of Technology, 2003. http://hdl.handle.net/1721.1/29294.
Includes bibliographical references.
A host of vital, current, and developing technologies, such as pyrolysis, thermal cracking, partial oxidation, and high-efficiency combustion engines, involve complex, gas-phase chemical mechanisms with hundreds of species and thousands of reactions. Building complete, explicit chemical models by-hand for these systems is exceedingly difficult. The bias and intuition of the developers figure strongly in the resultant mechanism, causing important but unanticipated pathways to be ignored, and useless pathways to be included. Thus many chemists and engineers have tried artificial intelligence software tools, or "automated mechanism generators", to build large chemical mechanisms systematically. These tools employ graph-theory algebra, and "rate rules" - estimates of rate constants for classes of reactions - to construct automatically all the possibly important reactions and species for a given set of conditions. All of these tools have been severely hampered by their inability to capture the effects of pressure-dependence and falloff - even though these effects are important in almost every gas-phase system of interest to engineers and designers. Pressure-dependent reactions cannot be included using simple rate rules. Until now they presented an unresolved quandary for automated mechanism generators. This work presents the first automated method for including pressure-dependent reactions generally and systematically, on-the-fly, in computerized mechanism generation.
(cont.) The approach includes in the mechanism only those pressure-dependent pathways important for the conditions of interest, but can find any potentially important pressure-dependent reaction. It works by building partial pressure-dependent reaction networks, step-by-step, in harmony with a rate-based termination criteria which rationally controls overall mechanism size. It uses a fast, approximate method, the Quantum-Rice-Ramsperger-Kassel/Modified-Strong-Collision (QRRK/MSC), to predict rate constants k(T,P) employing only high-pressure-limit rate rules, pressure-dependent network structure, and heat capacity estimates. The error incurred by screening the pressure- dependent networks to include only important sections is small and bounded. Successful applications to various systems, including reactions through cycloalkyl intermediates, are presented. Application of this tool to methane pyrolysis revealed a new, unexpected mechanism. It explained the decades-old mystery of methane autocatalysis at low conversion, a phenomenon which had defied all "by-hand" attempts at mechanism development. Such work hints at the predictive power inherent in the next generation of automated mechanism builders.
by David M. Matheu.
Ph.D.
Crump, Brian R. "Kinetic study of the mechanism and side reactions in the hydrogen peroxide based production of chlorine dioxide." Diss., Georgia Institute of Technology, 1998. http://hdl.handle.net/1853/11322.
Pope, Christopher James. "A chemical mechanism for fullerenes C₆₀ and C₇₀ formation with kinetic modeling of their synthesis in flames." Thesis, Massachusetts Institute of Technology, 1993. http://hdl.handle.net/1721.1/12663.
Tripathi, Rupali [Verfasser], Heinz Günter [Akademischer Betreuer] Pitsch, and S. Mani [Akademischer Betreuer] Sarathy. "Detailed chemical kinetic modeling of biofuels and their blends with conventional fuel components / Rupali Tripathi ; Heinz Pitsch, S. Mani Sarathy." Aachen : Universitätsbibliothek der RWTH Aachen, 2019. http://nbn-resolving.de/urn:nbn:de:101:1-2020080423315879685573.
Tripathi, Rupali Verfasser], Heinz Günter [Akademischer Betreuer] [Pitsch, and S. Mani [Akademischer Betreuer] Sarathy. "Detailed chemical kinetic modeling of biofuels and their blends with conventional fuel components / Rupali Tripathi ; Heinz Pitsch, S. Mani Sarathy." Aachen : Universitätsbibliothek der RWTH Aachen, 2019. http://d-nb.info/1215171676/34.
Savage, Nicholas. "The use of a modified IQT™ apparatus and detailed chemical kinetic model to investigate the atmospheric autoignition characteristics of model fuels." Master's thesis, University of Cape Town, 2009. http://hdl.handle.net/11427/5474.
Mallick, Sushanta. "Kinetic mechanism of NAD-malic enzyme from Ascaris suum in the direction of reductive carboxylation of pyruvate." Thesis, University of North Texas, 1990. https://digital.library.unt.edu/ark:/67531/metadc332658/.
Elias, Robert M. "The chemical reactivity of thermo mechanical pulp (TMP) fibres : a detailed kinetic study of the reaction between fibre and isolated fractions of hollcellulose and cellulose with succinic anhydride." Thesis, Bangor University, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239884.
Poon, Hiew Mun. "Development of integrated chemical kinetic mechanism reduction scheme for diesel and biodiesel fuel surrogates for multi-dimensional CFD applications." Thesis, University of Nottingham, 2016. http://eprints.nottingham.ac.uk/33980/.
Liu, Zhouyang. "Heterogeneous Catalytic Elemental Mercury Oxidation in Coal Combustion Flue Gas." University of Cincinnati / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1512045805884364.
Boz, Nezahat. "Kinetic Studies For The Production Of Tertiary Ethers Used As Gasoline Additives." Phd thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/12605039/index.pdf.
lSen Dogu June 2004, 174 pages In the present study, the kinetics studies for etherification reactions were investigated in detail. In the first phase of present study, different acidic resin catalysts were prepared by the heat treatment of Amberlyst-15 catalysts at 220°
C at different durations of time and also by the synthesis of sulfonated styrene divinylbenzene cross-linked resins at different conditions. A linear dependence of reaction rate on hydrogen ion-exchange capacity was in 2M2B+ethanol reaction. However, in the case of 2M1B+ethanol reaction hydrogen ion-exchange capacities over 2.8 meq.H+/g did not cause further increase in reaction rate, which was concluded to be majorly due to significance of diffusional resistances. DRIFTS experiments carried out with alcohols, isobutylene, isoamylenes and TAME (tert-amyl-methyl-ether) in a temperature range of 333-353 K supported a Langmuir-Hinshelwood type reaction mechanism involving adsorbed isoolefins molecules forming a bridged structure between &ndash
SO3H sites of the catalyst and adsorbed alcohol molecules. A rate expression derived basing on the mechanism proposed from the DRIFTS results gave good agreement with the published data. Reaction rate was found to give a sharp maximum at ethanol activity of around 0.1. The third phase of this work included evaluation of effective diffusivities and adsorption equilibrium constants of methanol, ethanol and 2M2B, in Amberlyst-15 from moment analysis of batch adsorber dynamic results. Models proposed for monodisperse and bidisperse pore structures were used for the evaluation of effective diffusivities. It was shown that surface diffusion contribution was quite significant. In the last phase of the work, a batch Reflux-Recycle-Reactor (RRR) was proposed, modeled and constructed to achieve high yields and selectivities in equilibrium limited reactions. The batch reflux recycle reactor was modeled by assuming plug flow in the reactor section, perfect mixing in the reboiler and vapor-liquid equilibria between the liquid in the reboiler and reactor inlet stream. In this system conversion values of isoamylenes reaching to 0.91 were achieved at 82°
C with almost 100% selectivity. Such conversion values were shown to be much higher than the corresponding equilibrium values that could be obtained in vapor phase fixed bed reactors. The activation energies evaluated in this system were found to be much less than the activation energies evaluated in the fixed bed reactor studies. This was concluded to be majorly due to the significance of transport resistant in the batch Reflux-Recycle-Reactor in which catalyst particles are partially wet. As a result of catalyst development, characterization, kinetic and reactor development studies carried out in this study, it was concluded that tert-amyl-ethyl-ether (TAEE) could be effectively produced and used as a gasoline blending oxygenate.
Fox, Clayton D. L. "Modeling Simplified Reaction Mechanisms using Continuous Thermodynamics for Hydrocarbon Fuels." Thesis, Université d'Ottawa / University of Ottawa, 2018. http://hdl.handle.net/10393/37554.
Sirjean, Baptiste. "Étude cinétique de réactions de pyrolyse et de combustion d'hydrocarbures cycliques par les approches de chimie quantique." Thesis, Vandoeuvre-les-Nancy, INPL, 2007. http://www.theses.fr/2007INPL093N/document.
Petroleum fuels are the world’s most important primary energy source and the need to maintain their supply is a major actual challenge involving both economical and environmental features. Decreasing fuels consumption is one of the more efficient ways to reconcile the goals of energy price and environmental protection. Numerical simulations become therefore a very important tool to optimize fuels and motors. Detailed chemical kinetic models are required to reproduce the reactivity of fuels and to characterize the amount of emitted pollutants. Such models imply a very large number of chemical species and elementary reactions, for a given species, and the determination of thermodynamic and kinetic data is a critical problem. Nowadays, quantum chemistry methods are able to calculate accurately thermodynamic data for a large number of chemical systems and to elucidate the reactivity of these systems. In this work we have used quantum chemistry to study the unimolecular reactions (initiation, molecular reactions, ß-scissions, cyclic ethers formations) involved in the decomposition of monocyclic and polycyclic hydrocarbons. From the results of quantum chemical calculations, a detailed chemical kinetic mechanism of the pyrolysis of a polycyclic alkane has been developed and validated against experimental data
Kim, Youngseob. "Air quality modeling : evaluation of chemical and meteorological parameterizations." Phd thesis, Université Paris-Est, 2011. http://pastel.archives-ouvertes.fr/pastel-00667777.
Chatelain, Karl. "Etude de la stabilité à l'oxydation des carburants en phase liquide." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLY020/document.
Liquid phase stability is a major concern in the transportation and the energy fields. Relevant examples are fuels, lubricants and additives which have to be stable from their production to their application (engine, combustors). This thesis aims to develop and validate a complete methodology combining both experimental data acquisition and the development of kinetic models for liquid phase autoxidation.The experimental methodology is based on a complementary approach to obtain (i) a global reactivity descriptor (Induction Periods) and (ii) detailed species profiles respectively using a PetroOxy device and an instrumented autoclave. Numerically, the presented methodology includes detailed liquid phase mechanisms generation with an automatic mechanism generator (RMG). Normal and iso-paraffins were selected as fuel surrogates for autoxidation to validate the developed methodology. They were selected regarding their large contribution in fuel composition and their growing interest as drop-in fuels.The reactivity of both n-paraffins from C8 to C16 and several C8 iso-paraffins was investigated over a wide temperature range (373-433 K) in the PetroOxy with liquid phase analyses. Then, detailed species profiles from the autoxidation of both n-octane and 2-methylheptane in autoclave were obtained at 383 K and 10 bars. Detailed liquid phase mechanisms were developed for all molecules tested up to C14. Mechanisms qualitatively reproduce the overall phenomenology of the chain length, the branching and the major species profiles observed experimentally. Mechanisms analysis allow to identify the main consumption pathways of alkanes through peroxy (ROO) and peroxy-hydroperoxide radicals (HOOQOO) over the temperature range investigated (373-473 K).This study permitted to increase the comprehension of autoxidation processes involved in normal and branched alkanes. The study of new chemical systems will increase the global comprehension of autoxidation processes and in fine it will reduce the gap between the current autoxidation knowledge and the real fuel autoxidation
Diaz, Aldana Luis A. "Mathematical Modeling of Ammonia Electro-Oxidation on Polycrystalline Pt DepositedElectrodes." Ohio University / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1395077873.
Chatelain, Karl. "Etude de la stabilité à l'oxydation des carburants en phase liquide." Electronic Thesis or Diss., Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLY020.
Liquid phase stability is a major concern in the transportation and the energy fields. Relevant examples are fuels, lubricants and additives which have to be stable from their production to their application (engine, combustors). This thesis aims to develop and validate a complete methodology combining both experimental data acquisition and the development of kinetic models for liquid phase autoxidation.The experimental methodology is based on a complementary approach to obtain (i) a global reactivity descriptor (Induction Periods) and (ii) detailed species profiles respectively using a PetroOxy device and an instrumented autoclave. Numerically, the presented methodology includes detailed liquid phase mechanisms generation with an automatic mechanism generator (RMG). Normal and iso-paraffins were selected as fuel surrogates for autoxidation to validate the developed methodology. They were selected regarding their large contribution in fuel composition and their growing interest as drop-in fuels.The reactivity of both n-paraffins from C8 to C16 and several C8 iso-paraffins was investigated over a wide temperature range (373-433 K) in the PetroOxy with liquid phase analyses. Then, detailed species profiles from the autoxidation of both n-octane and 2-methylheptane in autoclave were obtained at 383 K and 10 bars. Detailed liquid phase mechanisms were developed for all molecules tested up to C14. Mechanisms qualitatively reproduce the overall phenomenology of the chain length, the branching and the major species profiles observed experimentally. Mechanisms analysis allow to identify the main consumption pathways of alkanes through peroxy (ROO) and peroxy-hydroperoxide radicals (HOOQOO) over the temperature range investigated (373-473 K).This study permitted to increase the comprehension of autoxidation processes involved in normal and branched alkanes. The study of new chemical systems will increase the global comprehension of autoxidation processes and in fine it will reduce the gap between the current autoxidation knowledge and the real fuel autoxidation
Critchfield, Brian L. "Statistical Methods For Kinetic Modeling Of Fischer Tropsch Synthesis On A Supported Iron Catalyst." Diss., CLICK HERE for online access, 2006. http://contentdm.lib.byu.edu/ETD/image/etd1670.pdf.
Husson, Benoît. "Étude en réacteur auto-agité par jets gazeux de l'oxydation d'hydrocarbures naphténiques et aromatiques présents dans les gazoles." Thesis, Université de Lorraine, 2013. http://www.theses.fr/2013LORR0041/document.
The study of the oxidation of naphthenic (ethyl-cyclohexane,n-butyl-cyclohexane) and aromatic (ethyl-benzene,n-butyl-benzene, n-hexyl-benzene) hydrocarbons was performed in a jet-stirred reactor (pressure from 1 to10 bar, temperature from 500 to 1100 K, equivalenceratio: 0.25, 1 and2, residence time: 2s). Reaction products were quantified by gas chromatography and identified using mass spectrometry. The influence on the reactivity and the product selectivity of the equivalence ratio, the pressure and the size of the side alkyl chain attached tothe aromatic or naphthenic ringwas determined. The reactivity of ethyl-cyclohexane was also compared to that obtained for two other compounds containing 8 carbon atoms (n-octane and1-octene). The experimental results for ethyl-cyclohexane and n-butyl-benzene have been satisfactorily compared with prediction made using detailed kinetic mechanisms from the literature, except for the naphthenic at temperature below 800 K. A detailed kinetic mechanismfor the oxidation of ethyl-benzene has been developed (1411 reactions, 205 species) and validated from experimental results obtained in this studybut also from results available in literature. This mechanism has now becomethe "aromatic base" implemented in the software EXGAS Alkyl-aromaticswhich has been developed together with this PhD work and which allows theautomatic generation of alkyl-aromatics oxidation kinetic mechanisms. A study of the generic rules of decomposition of primary species in the secondary mechanism of this softwarewas conducted in this thesis
Tilland, Airy. "Étude de l’évolution de la réactivité des matériaux porteurs d’oxygène dans un procédé de combustion en boucle chimique." Thesis, Université de Lorraine, 2015. http://www.theses.fr/2015LORR0218/document.
The Chemical Looping Combustion (CLC) process produces energy by combustion of methane while capturing the carbon dioxide (CO2). An oxygen carrier (NiO/NiAl2O4) is used to deliver oxygen during the combustion of methane. It is then regenerated by air. The oxygen carrier material degrades over time, which increases the costs of the process and reduces its performance. The present study aims at determining the impacts of thermal and chemical phenomena on the oxygen carrier degradations. The reaction mechanisms corresponding to the reduction and oxidation of the oxygen carrier are determined and validated through experimental studies and the modeling of a continuously auto-stirred tank reactor (CASTR) and a plug flow reactor. The importance of controlling the quantity of deposited carbon in the process is illustrated. Then, the kinetic parameters of the reactions representing the reduction of nickel oxide are determined with an original model of the CASTR and validated in the plug flow reactor. The interest of using the CASTR for the determination of kinetic constants of the reactions involved in CLC process is presented. The obtained parameters give a good description of all reactions even if additional work is required to obtain a better precision of the results. Finally, a degradation mechanism of the oxygen carrier has been proposed. This mechanism describes the large production of fine particles separated from the grains and their role in the observed agglomeration phenomena. The support material, supposed to be inert, provides some of its oxygen. The methodology developed in this work could be adapted for the analysis and the characterization of other oxygen-carriers
Lannuzel, Frédéric. "Influence des aromatiques sur la stabilité thermique des pétroles dans les gisements." Phd thesis, Institut National Polytechnique de Lorraine - INPL, 2007. http://tel.archives-ouvertes.fr/tel-00473215.
Tang, Shiao-Shek, and 唐嘯石. "Kinetic and Chemical Mechanism of Octopus Digestive Gland." Thesis, 1995. http://ndltd.ncl.edu.tw/handle/94741434429315370625.
Ravi, Kiran Mandapaka. "Development of noble metal catalysts and detailed kinetic models for CO oxidation and water gas shift reactions." Thesis, 2018. https://etd.iisc.ac.in/handle/2005/5488.
Woo, Joseph L. "Gas-Aerosol Model For Mechanism Analysis: Kinetic Prediction Of Gas- And Aqueous-Phase Chemistry Of Atmospheric Aerosols." Thesis, 2014. https://doi.org/10.7916/D81N7Z3G.
"Computational Analyses of Complex Flows with Chemical Reactions." Doctoral diss., 2012. http://hdl.handle.net/2286/R.I.14749.
Dissertation/Thesis
Ph.D. Aerospace Engineering 2012
Eser, Bekir Engin. "Spectroscopic and Kinetic Investigation of the Catalytic Mechanism of Tyrosine Hydroxylase." 2009. http://hdl.handle.net/1969.1/ETD-TAMU-2009-12-7355.
Xia, Guoyun. "Modeling secondary organic aerosol formation using a simple scheme in a 3-dimensional air quality model and performing systematic mechanism reduction for a detailed chemical system /." 2006. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR19790.
Typescript. Includes bibliographical references (leaves 271-296). Also available on the Internet. MODE OF ACCESS via web browser by entering the following URL: http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:NR19790
Clancy, Kathleen. "Determination of the Kinetic and Chemical Mechanism of a Unique Peptidoglycan Recycling Enzyme with Dual Hydrolase and Kinase Functionality: Anhydromuramic Acid Kinase, AnmK." Diss., 2012. http://hdl.handle.net/10161/5820.
Antibiotic resistance is a crisis in modern society causing increasing rates of bacterial infections impervious to current therapies. To this end, new targets for antimicrobial treatment must be pursued. Peptidoglycan recycling is an understudied key life process in the bacterial cell where over 60% of cell wall materials are reused during each turnover. Anhydro-N-acetylmuramic acid kinase, AnmK is a novel enzyme in this pathway catalyzing the conversion of anhydro-N-acetylmuramic acid to N-acetylacetylmuramic acid-6-phosphate in the presence of magnesium and ATP. Previously, several crystal structures of AnmK have been solved providing insights into the catalytic mechanism, but until this point, no extensive work has been done. The goal of this work is to determine the chemical and kinetic mechanisms of AnmK. This will be completed using a continuous assay for dual hydrolysis and phosphorylation activity as well as a novel assay for carbohydrate hydrolysis. Substrate interactions will be probed using previous crystal structures as a guide. Finally, pre-steady-state studies will conclude the mechanistic studies giving a full depiction of AnmK catalysis.
The kinetic and chemical mechanisms of AnmK are studied in the steady-state using a continuous assay format where bisubstrate kinetics as well as inhibitor studies were performed as well as substrate specificity studies. pH rate profiles and solvent isotope exchange were used to determine the residues involved in catalysis.
The concerted or stepwise nature of hydrolysis and phosphorylation is a main question of this work. A novel assay using glucose oxidase was executed to trap any chemical intermediates formed in a potential stepwise reaction. This assay was used on wild-type AnmK as well as a variety of mutants. Through these experiments, two key residues in phosphoryl transfer are identified and used to partially decouple hydrolysis and phosphorylation.
Mechanistic studies were continued by investigating the pre-steady-state kinetics of AnmK using a quench flow apparatus. Wild-type AnmK showed no appearance of a chemical intermediate during timepoints as short as 10 ms and also showed a linear formation of product with a catalytic rate analogous to the steady-state rate. These results indicate that AnmK undergoes a concerted, one-step catalytic mechanism with no chemical intermediate. AnmK E330A formed both hydrolysis product, as well as hydrolysis and phosphorylation product in the pre-steady-state agreeing with the previous results that hydrolysis and phosphorylation had been partially decoupled.
These results show the chemical and kinetic mechanism of a novel enzyme with previously undocumented concomitant hydrolysis and phosphorylation. This work provides further understanding of carbohydrate-modifying enzymes as well as the peptidoglycan recycling pathway. A better understanding of peptidoglycan biosynthesis and recycling could lead to novel antimicrobial therapies in the future.
Dissertation