Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas

Detalhes bibliográficos
Autor(a) principal: Machado, Gladson de Souza
Data de Publicação: 2020
Tipo de documento: Tese
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UFRRJ
Texto Completo: https://rima.ufrrj.br/jspui/handle/20.500.14407/10254
Resumo: O presente trabalho tem por objetivo a investigação da ação de modelos da cinética química teórica para o tratamento de problemas relacionados química de combustões. Para tanto, quatro casos distintos foram estudados. No primeiro, a reação de abstração de hidrogênio do formaldeído por radicais hidroxila foi investigada em nível CCSD(T)/CBS, sendo localizado um complexo pré-barreira e um ponto de sela estabilizados por 3,31 e 1,35 kcal mol-1 em relação aos reagentes, respectivamente. Porém, a formação do complexo pré-barreira em temperaturas acima de 550 K se mostra um processo endergônico em relação à energia livre de Gibbs. Portanto, acima deste valor de temperatura a reação pode ser considerada elementar, sendo indicado o cálculo dos coeficientes de velocidade pela teoria do estado de transição variacional canônica. No segundo estudo de caso foi feita a investigação cinética da decomposição do ácido fórmico. Embora as duas principais vias, descarboxilação e desidratação, tenham apresentado valores muito semelhantes de barreira, 65,40 e 65,03 kcal mol-1, respectivamente, em nível CCSD(T)/CBS, a preferência majoritária pela via de desidratação pode ser explicada pela reação de isomerização entre os confôrmeros Z e E. O coeficiente de velocidade da reação de formação do confôrmero Z é sempre maior que a do outro confôrmero. Além disso, através de cálculos de coeficiente de velocidade RRKM e posterior solução da equação mestra, foi constatado que a transição do regime de segunda ordem para o regime falloff ocorre em 0,5 atm a 1400 K. No terceiro estudo de caso foram investigadas cinco reações de iniciação da combustão da acetona, quatro unimoleculares e uma bimolecular, sendo essa de abstração de hidrogênio por oxigênio molecular. Essas reações foram analisadas em nível CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ. Coeficientes de velocidade foram calculados através da teoria RRKM com posterior solução da equação mestra, para as reações unimoleculares e para a reação bimolecular foi utilizada a teoria do estado de transição canônica. A reação de dissociação, através da quebra de ligação C-C, se mostrou a principal via dentre as unimoleculares. Após o mecanismo de combustão proposto por Sarathy ser otimizado com os parâmetros cinéticos calculados para a acetona, o erro em relação ao tempo de ignição foi reduzido de 81% para 24%. Por fim, no quarto estudo de caso, foram feitas simulações 0D de um ciclo Otto ideal com os seguintes combustíveis: acetona, butanol, etanol, butanol/etanol e acetona/butanol/etanol. Para isso foi proposto um modelo de centelha através da dissociação de 5% do oxigênio e dos combustíveis. Nas integrações do mecanismo de combustão, a análise de velocidades das reações demonstrou que todos os combustíveis são iniciados majoritariamente pela reação de átomos de oxigênio com radicais metil, gerando formaldeído e átomos de hidrogênio. Estes átomos passam por algumas etapas até a formação de radicais hidroxila, que reagem com os combustíveis através de reações de abstração de hidrogênio. Feitas as análises dos estudos de caso, conclui-se que a escolha do método mecânico quântico aliada à termodinâmica, ao modelo cinético adequado e análises numéricas gerou resultados satisfatórios, capazes de propor soluções para discussões em aberto na literatura, novos coeficientes de velocidade e interpretações provenientes de um mecanismo de combustão
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spelling Machado, Gladson de SouzaBauerfeldt, Glauco Favilla069.023.487-23https://orcid.org/0000-0001-5906-7080http://lattes.cnpq.br/1876040291299143Bauerfeldt, Glauco Favilla069.023.487-23https://orcid.org/0000-0001-5906-7080http://lattes.cnpq.br/1876040291299143Silva, Clarissa Oliveira dahttps://orcid.org/0000-0002-5640-5387http://lattes.cnpq.br/3211933004567550Sant'Anna, Carlos Mauricio Rabello dehttps://orcid.org/0000-0003-1989-5038http://lattes.cnpq.br/2087099684752643Klachquin, Graciela Arbilla dehttps://orcid.org/0000-0001-7732-8336http://lattes.cnpq.br/7712800981237085Faria, Roberto de Barroshttp://lattes.cnpq.br/6310881885990978058.310.287-55http://lattes.cnpq.br/35843482343630332023-12-21T18:59:38Z2023-12-21T18:59:38Z2020-03-06MACHADO, Gladson de Souza. Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas. 2020. 115 f. Tese (Doutorado em Química) - Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, 2020.https://rima.ufrrj.br/jspui/handle/20.500.14407/10254O presente trabalho tem por objetivo a investigação da ação de modelos da cinética química teórica para o tratamento de problemas relacionados química de combustões. Para tanto, quatro casos distintos foram estudados. No primeiro, a reação de abstração de hidrogênio do formaldeído por radicais hidroxila foi investigada em nível CCSD(T)/CBS, sendo localizado um complexo pré-barreira e um ponto de sela estabilizados por 3,31 e 1,35 kcal mol-1 em relação aos reagentes, respectivamente. Porém, a formação do complexo pré-barreira em temperaturas acima de 550 K se mostra um processo endergônico em relação à energia livre de Gibbs. Portanto, acima deste valor de temperatura a reação pode ser considerada elementar, sendo indicado o cálculo dos coeficientes de velocidade pela teoria do estado de transição variacional canônica. No segundo estudo de caso foi feita a investigação cinética da decomposição do ácido fórmico. Embora as duas principais vias, descarboxilação e desidratação, tenham apresentado valores muito semelhantes de barreira, 65,40 e 65,03 kcal mol-1, respectivamente, em nível CCSD(T)/CBS, a preferência majoritária pela via de desidratação pode ser explicada pela reação de isomerização entre os confôrmeros Z e E. O coeficiente de velocidade da reação de formação do confôrmero Z é sempre maior que a do outro confôrmero. Além disso, através de cálculos de coeficiente de velocidade RRKM e posterior solução da equação mestra, foi constatado que a transição do regime de segunda ordem para o regime falloff ocorre em 0,5 atm a 1400 K. No terceiro estudo de caso foram investigadas cinco reações de iniciação da combustão da acetona, quatro unimoleculares e uma bimolecular, sendo essa de abstração de hidrogênio por oxigênio molecular. Essas reações foram analisadas em nível CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ. Coeficientes de velocidade foram calculados através da teoria RRKM com posterior solução da equação mestra, para as reações unimoleculares e para a reação bimolecular foi utilizada a teoria do estado de transição canônica. A reação de dissociação, através da quebra de ligação C-C, se mostrou a principal via dentre as unimoleculares. Após o mecanismo de combustão proposto por Sarathy ser otimizado com os parâmetros cinéticos calculados para a acetona, o erro em relação ao tempo de ignição foi reduzido de 81% para 24%. Por fim, no quarto estudo de caso, foram feitas simulações 0D de um ciclo Otto ideal com os seguintes combustíveis: acetona, butanol, etanol, butanol/etanol e acetona/butanol/etanol. Para isso foi proposto um modelo de centelha através da dissociação de 5% do oxigênio e dos combustíveis. Nas integrações do mecanismo de combustão, a análise de velocidades das reações demonstrou que todos os combustíveis são iniciados majoritariamente pela reação de átomos de oxigênio com radicais metil, gerando formaldeído e átomos de hidrogênio. Estes átomos passam por algumas etapas até a formação de radicais hidroxila, que reagem com os combustíveis através de reações de abstração de hidrogênio. Feitas as análises dos estudos de caso, conclui-se que a escolha do método mecânico quântico aliada à termodinâmica, ao modelo cinético adequado e análises numéricas gerou resultados satisfatórios, capazes de propor soluções para discussões em aberto na literatura, novos coeficientes de velocidade e interpretações provenientes de um mecanismo de combustãoCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível SuperiorThis work aims to investigate the action of theoretical chemical kinetics models for the treatment of combustion chemistry related problems. Four different cases were studied. In the first case, the hydrogen abstraction reaction channel in the formaldehyde + hydroxyl radicals reaction mechanism was investigated at the CCSD(T)/CBS level, with a pre-barrier complex and a saddle point stabilized by 3.31 and 1.35 kcal mol-1 with respect to the reactants, respectively. However, Gibbs free energy profile suggests that the formation of the pre-barrier complex at temperatures above 550 K is an endergonic process. Therefore, above this temperature value the reaction can be considered elementary, and the calculation of the rate coefficients is suggested by the canonical variational transition state theory method. In the second case study, the kinetic investigation of the decomposition of formic acid was carried out. Although the two main pathways, decarboxylation and dehydration, presented very similar barrier values, 65.40 and 65.03 kcal mol-1, respectively, at the CCSD(T)/CBS level, the prevalence of the dehydration pathway can be explained by the isomerization reaction between the Z and E conformers. The rate coefficient for the formation of the Z-conformer is always higher than that for the other conformer. Furthermore, through RRKM calculations and subsequent solution of the master equation, it was found that the transition from the second order regime to the falloff regime occurs at 0.5 atm at 1400 K. In the third case study, five initiation steps in acetone combustion mechanism were investigated: four unimolecular reactions and one bimolecular reaction, the latter being the abstraction of hydrogen by molecular oxygen. These reactions were analyzed at the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ level. Rate coefficients were calculated using the RRKM theory with subsequent solution of the master equation, for the unimolecular reactions and for the bimolecular reaction the canonical transition state theory was applied. The dissociation reaction, breaking of the C-C bond, proved to be the main route among the unimolecular steps. The combustion mechanism proposed by Sarathy was optimized by the insertion of the calculated kinetic parameters calculated for acetone, and the error in the prediction of ignition time was reduced from 81% to 24%. Finally, in the fourth case study, 0D simulations of an ideal Otto cycle were performed with the following fuels: acetone, butanol, ethanol, butanol/ethanol and acetone/butanol/ethanol. A spark model was proposed through the dissociation of 5% of oxygen and fuels. In the integration of the combustion mechanism, the analysis of reaction rates demonstrated that all fuels are mainly initiated by the reaction of oxygen atoms with methyl radicals, generating formaldehyde and hydrogen atoms. These atoms pass through some stages until the formation of hydroxyl radicals, which react with the fuels through hydrogen abstraction reactions. After analyzing the case studies, it is concluded that the choice of the quantum mechanical method combined with thermodynamics, the appropriate kinetic model and numerical analyzes generated satisfactory results, capable of proposing solutions for open discussions in the literature, new rate coefficients and interpretations from a combustion mechanismapplication/pdfporUniversidade Federal Rural do Rio de JaneiroPrograma de Pós-Graduação em QuímicaUFRRJBrasilInstituto de QuímicaCombustãoFormaldeídoÁcido fórmicoAcetonaButanolCombustionFormaldehydeFormic AcidAcetoneButanolQuímicaInvestigações na química de combustões usando modelos da cinética química teórica e simulações numéricasInvestigations in the chemistry of combustion using models of theoretical chemical kinetics and numerical simulationsinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisABO, B. O., GAO, M., WANG, Y., et al. 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ZHU, Y., DAVIDSON, D. F., HANSON, R. K. "1-Butanol ignition delay times at low temperatures: An application of the constrained-reaction-volume strategy", Combustion 115 and Flame, v. 161, n. 3, p. 634–643, mar. 2014. DOI: 10.1016/j.combustflame.2013.06.028. .https://tede.ufrrj.br/retrieve/71565/2020%20-%20Gladson%20de%20Souza%20Machado.pdf.jpghttps://tede.ufrrj.br/jspui/handle/jspui/6176Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2023-01-03T11:50:13Z No. of bitstreams: 1 2020 - Gladson de Souza Machado.pdf: 3256825 bytes, checksum: c4af84c4c54eab3fc4f44202fc830921 (MD5)Made available in DSpace on 2023-01-03T11:50:14Z (GMT). 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dc.title.por.fl_str_mv Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
dc.title.alternative.eng.fl_str_mv Investigations in the chemistry of combustion using models of theoretical chemical kinetics and numerical simulations
title Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
spellingShingle Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
Machado, Gladson de Souza
Combustão
Formaldeído
Ácido fórmico
Acetona
Butanol
Combustion
Formaldehyde
Formic Acid
Acetone
Butanol
Química
title_short Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
title_full Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
title_fullStr Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
title_full_unstemmed Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
title_sort Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas
author Machado, Gladson de Souza
author_facet Machado, Gladson de Souza
author_role author
dc.contributor.author.fl_str_mv Machado, Gladson de Souza
dc.contributor.advisor1.fl_str_mv Bauerfeldt, Glauco Favilla
dc.contributor.advisor1ID.fl_str_mv 069.023.487-23
https://orcid.org/0000-0001-5906-7080
dc.contributor.advisor1Lattes.fl_str_mv http://lattes.cnpq.br/1876040291299143
dc.contributor.referee1.fl_str_mv Bauerfeldt, Glauco Favilla
dc.contributor.referee1ID.fl_str_mv 069.023.487-23
https://orcid.org/0000-0001-5906-7080
dc.contributor.referee1Lattes.fl_str_mv http://lattes.cnpq.br/1876040291299143
dc.contributor.referee2.fl_str_mv Silva, Clarissa Oliveira da
dc.contributor.referee2ID.fl_str_mv https://orcid.org/0000-0002-5640-5387
dc.contributor.referee2Lattes.fl_str_mv http://lattes.cnpq.br/3211933004567550
dc.contributor.referee3.fl_str_mv Sant'Anna, Carlos Mauricio Rabello de
dc.contributor.referee3ID.fl_str_mv https://orcid.org/0000-0003-1989-5038
dc.contributor.referee3Lattes.fl_str_mv http://lattes.cnpq.br/2087099684752643
dc.contributor.referee4.fl_str_mv Klachquin, Graciela Arbilla de
dc.contributor.referee4ID.fl_str_mv https://orcid.org/0000-0001-7732-8336
dc.contributor.referee4Lattes.fl_str_mv http://lattes.cnpq.br/7712800981237085
dc.contributor.referee5.fl_str_mv Faria, Roberto de Barros
dc.contributor.referee5Lattes.fl_str_mv http://lattes.cnpq.br/6310881885990978
dc.contributor.authorID.fl_str_mv 058.310.287-55
dc.contributor.authorLattes.fl_str_mv http://lattes.cnpq.br/3584348234363033
contributor_str_mv Bauerfeldt, Glauco Favilla
Bauerfeldt, Glauco Favilla
Silva, Clarissa Oliveira da
Sant'Anna, Carlos Mauricio Rabello de
Klachquin, Graciela Arbilla de
Faria, Roberto de Barros
dc.subject.por.fl_str_mv Combustão
Formaldeído
Ácido fórmico
Acetona
Butanol
topic Combustão
Formaldeído
Ácido fórmico
Acetona
Butanol
Combustion
Formaldehyde
Formic Acid
Acetone
Butanol
Química
dc.subject.eng.fl_str_mv Combustion
Formaldehyde
Formic Acid
Acetone
Butanol
dc.subject.cnpq.fl_str_mv Química
description O presente trabalho tem por objetivo a investigação da ação de modelos da cinética química teórica para o tratamento de problemas relacionados química de combustões. Para tanto, quatro casos distintos foram estudados. No primeiro, a reação de abstração de hidrogênio do formaldeído por radicais hidroxila foi investigada em nível CCSD(T)/CBS, sendo localizado um complexo pré-barreira e um ponto de sela estabilizados por 3,31 e 1,35 kcal mol-1 em relação aos reagentes, respectivamente. Porém, a formação do complexo pré-barreira em temperaturas acima de 550 K se mostra um processo endergônico em relação à energia livre de Gibbs. Portanto, acima deste valor de temperatura a reação pode ser considerada elementar, sendo indicado o cálculo dos coeficientes de velocidade pela teoria do estado de transição variacional canônica. No segundo estudo de caso foi feita a investigação cinética da decomposição do ácido fórmico. Embora as duas principais vias, descarboxilação e desidratação, tenham apresentado valores muito semelhantes de barreira, 65,40 e 65,03 kcal mol-1, respectivamente, em nível CCSD(T)/CBS, a preferência majoritária pela via de desidratação pode ser explicada pela reação de isomerização entre os confôrmeros Z e E. O coeficiente de velocidade da reação de formação do confôrmero Z é sempre maior que a do outro confôrmero. Além disso, através de cálculos de coeficiente de velocidade RRKM e posterior solução da equação mestra, foi constatado que a transição do regime de segunda ordem para o regime falloff ocorre em 0,5 atm a 1400 K. No terceiro estudo de caso foram investigadas cinco reações de iniciação da combustão da acetona, quatro unimoleculares e uma bimolecular, sendo essa de abstração de hidrogênio por oxigênio molecular. Essas reações foram analisadas em nível CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ. Coeficientes de velocidade foram calculados através da teoria RRKM com posterior solução da equação mestra, para as reações unimoleculares e para a reação bimolecular foi utilizada a teoria do estado de transição canônica. A reação de dissociação, através da quebra de ligação C-C, se mostrou a principal via dentre as unimoleculares. Após o mecanismo de combustão proposto por Sarathy ser otimizado com os parâmetros cinéticos calculados para a acetona, o erro em relação ao tempo de ignição foi reduzido de 81% para 24%. Por fim, no quarto estudo de caso, foram feitas simulações 0D de um ciclo Otto ideal com os seguintes combustíveis: acetona, butanol, etanol, butanol/etanol e acetona/butanol/etanol. Para isso foi proposto um modelo de centelha através da dissociação de 5% do oxigênio e dos combustíveis. Nas integrações do mecanismo de combustão, a análise de velocidades das reações demonstrou que todos os combustíveis são iniciados majoritariamente pela reação de átomos de oxigênio com radicais metil, gerando formaldeído e átomos de hidrogênio. Estes átomos passam por algumas etapas até a formação de radicais hidroxila, que reagem com os combustíveis através de reações de abstração de hidrogênio. Feitas as análises dos estudos de caso, conclui-se que a escolha do método mecânico quântico aliada à termodinâmica, ao modelo cinético adequado e análises numéricas gerou resultados satisfatórios, capazes de propor soluções para discussões em aberto na literatura, novos coeficientes de velocidade e interpretações provenientes de um mecanismo de combustão
publishDate 2020
dc.date.issued.fl_str_mv 2020-03-06
dc.date.accessioned.fl_str_mv 2023-12-21T18:59:38Z
dc.date.available.fl_str_mv 2023-12-21T18:59:38Z
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/doctoralThesis
format doctoralThesis
status_str publishedVersion
dc.identifier.citation.fl_str_mv MACHADO, Gladson de Souza. Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas. 2020. 115 f. Tese (Doutorado em Química) - Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, 2020.
dc.identifier.uri.fl_str_mv https://rima.ufrrj.br/jspui/handle/20.500.14407/10254
identifier_str_mv MACHADO, Gladson de Souza. Investigações na química de combustões usando modelos da cinética química teórica e simulações numéricas. 2020. 115 f. Tese (Doutorado em Química) - Instituto de Química, Universidade Federal Rural do Rio de Janeiro, Seropédica, 2020.
url https://rima.ufrrj.br/jspui/handle/20.500.14407/10254
dc.language.iso.fl_str_mv por
language por
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