Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa
Ano de defesa: | 2016 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , |
Tipo de documento: | Dissertação |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/11976 |
Resumo: | Electrospray ionization mass spectrometry (ESI-MS) with induced collision energy was used to carry out a comprehensive study on the interaction energies between cations and anions of dicationic ionic liquids. The influence of the anion ([Br]-, [NO3]-, [BF4]-, [SCN]- and [Cl]-) and the size of alkyl chain (n = 4,6,8 and 10) in the interaction energy of ionic liquids derived from the 1, n-bis (3-methylimidazolyl-1-yl) alkane with n = 4,6,8 and 10, in the gas phase was investigated. Three experiments were carried out to determine the cation-anion interaction energy: (i) ESI-MS of binary (1:1) mixtures of ionic liquids with different anions or cations; (Ii) ESI-MS of ionic liquid individually with variation of the applied collision energy and determination of the center of mass energy (Ecm) using the relation between the intensity of the precursor ion and the sum of the ions; (iii) the rate of variation of the intensity of the precursor ion as a function of collision energy at different concentrations of all ionic liquids was obtained. From this correlation, the cation-anion dissociation constant of the dicationic ionic liquids was obtained. The results showed the appearance of mixed species (example: [Bis-C8(MIM)22XY]- and [C8(MIM)XY]-) in the binary mixtures. The application of the induced collision energy in the mixtures allowed estimating which anion interacts more effectively with the cation. Also for this experiments, the dicationic ionic liquids with the anions [Cl]-, [Br]- and [NO3]- presented higher cation-anion interaction energy. The increasing order of interaction energy was [BF4]- <[SCN]- <[NO3]- <[Br]- <[Cl]-. The Ecm values for ionic liquids with different anions did not indicate trends in the interaction energy in relation to structural factors such as ionic radius and molecular volume. Thus, for the anions, it was found that the interaction increases in the following order: [SCN]- <[Cl]- <[NO3]- <[Br]- <[BF4]-. On the other hand, increasing the size of the spacer alkyl chain caused an increase in cation-anion interaction energy. As the concentration of the ionic liquid increased, an increase in the precursor ion intensity was observed. |
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2017-11-07T13:01:18Z2017-11-07T13:01:18Z2016-08-05http://repositorio.ufsm.br/handle/1/11976Electrospray ionization mass spectrometry (ESI-MS) with induced collision energy was used to carry out a comprehensive study on the interaction energies between cations and anions of dicationic ionic liquids. The influence of the anion ([Br]-, [NO3]-, [BF4]-, [SCN]- and [Cl]-) and the size of alkyl chain (n = 4,6,8 and 10) in the interaction energy of ionic liquids derived from the 1, n-bis (3-methylimidazolyl-1-yl) alkane with n = 4,6,8 and 10, in the gas phase was investigated. Three experiments were carried out to determine the cation-anion interaction energy: (i) ESI-MS of binary (1:1) mixtures of ionic liquids with different anions or cations; (Ii) ESI-MS of ionic liquid individually with variation of the applied collision energy and determination of the center of mass energy (Ecm) using the relation between the intensity of the precursor ion and the sum of the ions; (iii) the rate of variation of the intensity of the precursor ion as a function of collision energy at different concentrations of all ionic liquids was obtained. From this correlation, the cation-anion dissociation constant of the dicationic ionic liquids was obtained. The results showed the appearance of mixed species (example: [Bis-C8(MIM)22XY]- and [C8(MIM)XY]-) in the binary mixtures. The application of the induced collision energy in the mixtures allowed estimating which anion interacts more effectively with the cation. Also for this experiments, the dicationic ionic liquids with the anions [Cl]-, [Br]- and [NO3]- presented higher cation-anion interaction energy. The increasing order of interaction energy was [BF4]- <[SCN]- <[NO3]- <[Br]- <[Cl]-. The Ecm values for ionic liquids with different anions did not indicate trends in the interaction energy in relation to structural factors such as ionic radius and molecular volume. Thus, for the anions, it was found that the interaction increases in the following order: [SCN]- <[Cl]- <[NO3]- <[Br]- <[BF4]-. On the other hand, increasing the size of the spacer alkyl chain caused an increase in cation-anion interaction energy. As the concentration of the ionic liquid increased, an increase in the precursor ion intensity was observed.A espectrometria de massa com ionização por electrospray (ESI-MS) com energia de colisão induzida foi utilizada para realizar um estudo compreensivo sobre as energias de interação entre cátions e ânions de líquidos iônicos dicatiônicos. Foi avaliada a influência do ânion ([Br]-, [NO3]-, [BF4]-, [SCN]- e [Cl]-) e o tamanho da cadeia alquílica espaçadora (n=4,6,8 e 10) na energia de interação dos líquidos iônicos dicatiônicos, derivados do 1,n-bis(3-metilimidazolil-1-íneo)alcano em fase gasosa. Três experimentos foram realizados para a determinação da energia de interação cátion-ânion: (i) ESI-MS de misturas binárias (1:1) de líquidos iônicos com diferentes ânions ou cátions; (ii) ESI-MS de cada líquido iônico individualmente com variação da energia de colisão aplicada e determinação da energia de centro de massa (Ecm) usando a relação entre intensidade do íon precursor e somatório dos íons. (iii) Por fim, foi obtida a taxa de variação da intensidade do íon precursor em função energia de colisão de todos os líquidos iônicos. A partir desta correlação, foi obtida a constante de dissociação cátion-ânion dos líquidos iônicos dicatiônicos. Os resultados mostraram o aparecimento de espécies mistas (exemplo: [Bis-C8(MIM)22XY]- e [C8(MIM)XY]-) nos experimentos das misturas. A aplicação da energia de colisão induzida nas misturas também permitiu estimar qual ânion interage mais efetivamente com o cátion. Ainda para este experimentos, os líquidos iônicos dicatiônicos com os ânions [Cl]-, [Br]- e [NO3]- apresentaram maior energia de interação cátion-ânion. A escala em ordem crescente de energia de interação foi [BF4]-< [SCN]- < [NO3]- < [Br]- < [Cl]-. Os valores de Ecm para os líquidos iônicos com diferentes ânions não indicou tendências na energia de interação em relação fatores estruturais tais como raio iônico e volume molecular. Dessa forma, para os ânions, foi encontrado que a interação aumenta na seguinte ordem: [SCN]-<[Cl]-<[NO3]-<[Br]-<[BF4]-. Por outro lado, o aumento do tamanho da cadeia alquílica espaçadora causou um aumento na energia de interação cátion-ânion. Com o aumento da concentração do líquido iônico, foi observado um aumento na intensidade do íon precursor.porUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessLíquidos iônicos dicatiônicosEspectrometria de massaEnergia de centro de massaEnergia de colisão induzidaEnergia de interaçãoDicationic ionic liquidsMass spectrometryCenter-of-mass-energiesCollision induced energyInteraction energyCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAEnergia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosaInteraction energy of cation-anion in dicationic ionic liquids in the gas phaseinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisFrizzo, Clarissa Piccininhttp://lattes.cnpq.br/0029279904716491Martins, Marcos Antônio Pintohttp://lattes.cnpq.br/6457412713967642Villetti, Marcos Antoniohttp://lattes.cnpq.br/8504489050993642Machado, Pablohttp://lattes.cnpq.br/3319303431365448http://lattes.cnpq.br/2747518904757022Hennemann, Bruno Luís1006000000006008339c8fa-17c5-4531-bcb5-111d15cb015ce00fcd4e-e910-4d70-9b42-3c945b6f9bcb04e28df9-6f69-4ebd-9d47-5873727d6d43e6eb13a6-e907-4f66-a425-e079964588f6a2ca45d4-9762-4526-9260-c56e88fa871areponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUÍMICA_2016_HENNEMANN_BRUNO.pdfDIS_PPGQUÍMICA_2016_HENNEMANN_BRUNO.pdfDissertação de Mestradoapplication/pdf4528395http://repositorio.ufsm.br/bitstream/1/11976/1/DIS_PPGQU%c3%8dMICA_2016_HENNEMANN_BRUNO.pdf824eb2b902f50c5f3822f257bb600883MD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
dc.title.alternative.eng.fl_str_mv |
Interaction energy of cation-anion in dicationic ionic liquids in the gas phase |
title |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
spellingShingle |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa Hennemann, Bruno Luís Líquidos iônicos dicatiônicos Espectrometria de massa Energia de centro de massa Energia de colisão induzida Energia de interação Dicationic ionic liquids Mass spectrometry Center-of-mass-energies Collision induced energy Interaction energy CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
title_full |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
title_fullStr |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
title_full_unstemmed |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
title_sort |
Energia de interação cátion-ânion de líquidos iônicos dicatiônicos em fase gasosa |
author |
Hennemann, Bruno Luís |
author_facet |
Hennemann, Bruno Luís |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Frizzo, Clarissa Piccinin |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/0029279904716491 |
dc.contributor.advisor-co1.fl_str_mv |
Martins, Marcos Antônio Pinto |
dc.contributor.advisor-co1Lattes.fl_str_mv |
http://lattes.cnpq.br/6457412713967642 |
dc.contributor.referee1.fl_str_mv |
Villetti, Marcos Antonio |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/8504489050993642 |
dc.contributor.referee2.fl_str_mv |
Machado, Pablo |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/3319303431365448 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/2747518904757022 |
dc.contributor.author.fl_str_mv |
Hennemann, Bruno Luís |
contributor_str_mv |
Frizzo, Clarissa Piccinin Martins, Marcos Antônio Pinto Villetti, Marcos Antonio Machado, Pablo |
dc.subject.por.fl_str_mv |
Líquidos iônicos dicatiônicos Espectrometria de massa Energia de centro de massa Energia de colisão induzida Energia de interação |
topic |
Líquidos iônicos dicatiônicos Espectrometria de massa Energia de centro de massa Energia de colisão induzida Energia de interação Dicationic ionic liquids Mass spectrometry Center-of-mass-energies Collision induced energy Interaction energy CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Dicationic ionic liquids Mass spectrometry Center-of-mass-energies Collision induced energy Interaction energy |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Electrospray ionization mass spectrometry (ESI-MS) with induced collision energy was used to carry out a comprehensive study on the interaction energies between cations and anions of dicationic ionic liquids. The influence of the anion ([Br]-, [NO3]-, [BF4]-, [SCN]- and [Cl]-) and the size of alkyl chain (n = 4,6,8 and 10) in the interaction energy of ionic liquids derived from the 1, n-bis (3-methylimidazolyl-1-yl) alkane with n = 4,6,8 and 10, in the gas phase was investigated. Three experiments were carried out to determine the cation-anion interaction energy: (i) ESI-MS of binary (1:1) mixtures of ionic liquids with different anions or cations; (Ii) ESI-MS of ionic liquid individually with variation of the applied collision energy and determination of the center of mass energy (Ecm) using the relation between the intensity of the precursor ion and the sum of the ions; (iii) the rate of variation of the intensity of the precursor ion as a function of collision energy at different concentrations of all ionic liquids was obtained. From this correlation, the cation-anion dissociation constant of the dicationic ionic liquids was obtained. The results showed the appearance of mixed species (example: [Bis-C8(MIM)22XY]- and [C8(MIM)XY]-) in the binary mixtures. The application of the induced collision energy in the mixtures allowed estimating which anion interacts more effectively with the cation. Also for this experiments, the dicationic ionic liquids with the anions [Cl]-, [Br]- and [NO3]- presented higher cation-anion interaction energy. The increasing order of interaction energy was [BF4]- <[SCN]- <[NO3]- <[Br]- <[Cl]-. The Ecm values for ionic liquids with different anions did not indicate trends in the interaction energy in relation to structural factors such as ionic radius and molecular volume. Thus, for the anions, it was found that the interaction increases in the following order: [SCN]- <[Cl]- <[NO3]- <[Br]- <[BF4]-. On the other hand, increasing the size of the spacer alkyl chain caused an increase in cation-anion interaction energy. As the concentration of the ionic liquid increased, an increase in the precursor ion intensity was observed. |
publishDate |
2016 |
dc.date.issued.fl_str_mv |
2016-08-05 |
dc.date.accessioned.fl_str_mv |
2017-11-07T13:01:18Z |
dc.date.available.fl_str_mv |
2017-11-07T13:01:18Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/11976 |
url |
http://repositorio.ufsm.br/handle/1/11976 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
dc.relation.authority.fl_str_mv |
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dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
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UFSM |
institution |
UFSM |
reponame_str |
Biblioteca Digital de Teses e Dissertações do UFSM |
collection |
Biblioteca Digital de Teses e Dissertações do UFSM |
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MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1793240154795671552 |