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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2010.tde-10112010-103107
Document
Author
Full name
Fabio Rodrigues
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2010
Supervisor
Committee
Santos, Paulo Sérgio (President)
Araki, Koiti
Camilo, Fernanda Ferraz
Figueiredo Neto, Antonio Martins
Torresi, Roberto Manuel
Title in Portuguese
Espectroscopia Raman de líquidos iônicos imidazólicos: interações interiônicas, organização estrutural e efeitos de micro-ambiente
Keywords in Portuguese
Espectroscopia Raman
Imidazol
Interações interiônicas
Líquidos Iônicos
Sal fundido
Abstract in Portuguese
O presente trabalho tem como objetivo principal um estudo sistemático de líquidos iônicos imidazólicos, ou seja, sais líquidos a temperaturas relativamente baixas derivados do anel imidazol, tendo como técnica principal a espectroscopia Raman. Foram estudados os cátions 1-alquil-3- metilimidazólio e 1-alquil-2,3-dimetilimidazólio, sendo o grupo alquil composto por 2, 4, 6, 8 ou 10 átomos de carbono, com os ânions brometo, hexafluorofosfato ou bis(trifluorometanosulfonil)imida (TFSI-), totalizando 30 sistemas distintos. O estudo foi dividido em três partes. Na primeira, foram estudados compostos derivados de imidazol, neutros e catiônicos, para entender as diferenças entre os cátions formadores (o ânion foi desconsiderado) de ILs e seus precursores. A espectroscopia Raman forneceu informações sobre as alterações nos modos vibracionais com as substituições, sendo possível constatar que os modos do anel se tornaram menos intensos com as substituições e a contribuição de grupos -CH se tornou mais importante. Cálculos de cargas de Mulliken foram realizados para estas espécies e os resultados obtidos reforçam as interpretações dos espectros vibracionais. A segunda etapa consistiu no estudo de ILs puros, analisando tanto cátion quanto ânion. A cadeia carbônica tem grande influência no espectro Raman, sendo observadas bandas atribuídas a confôrmeros diferentes, que aparecem em maior número e menor intensidade à medida que a cadeia se torna menor. Os ânions foram estudados nos ILs e em sais inorgânicos, sendo observados espectros muito semelhantes destes nos diversos ILs, porém diferentes nos sais inorgânicos. Os mesmos resultados foram encontrados nas medidas de XANES (espectroscopia de raio-X próxima à borda de absorção), que permitiu sondar a estrutura eletrônica ao redor de diversos átomos, utilizada como técnica auxiliar. Após analisado cátions e ânions, foi possível caracterizar o par iônico formado por estes íons, enfocando as bandas Raman das cadeias carbônicas, já que, como a interação de Coulomb é baixa, estes se ligam principalmente via ligação de hidrogênio. Para os ILs com -H no carbono 2, o ânion Br- forma um par iônico mais forte com os diversos cátions, enquanto PF6- e TFSI-
Title in English
Raman Spectroscopy study of imidazolic ionic liquids: interionic interactions, structural organization and micro-environment effects
Keywords in English
Imidazole
Interionic interactions
Ionic Liquids
Molten salt.
Raman Spectroscopy
Abstract in English
The present work aims to be a systematic study, by Raman spectroscopy, of imidazolic ionic liquids, which means low temperature molten salts derived from imidazole ring. The study involved the cations 1-alkil-3-methylimidazolium and 1-alkyl-2,3-dimethylimidazolim, being alkyl chain composed of 2, 4, 6, 8 or 10 carbon atoms and with the anions bromide, hexafluorophosphate and bis(trifluoromethanesulfonyl)imide (TFSI-), in a grand total of 30 species with distinct properties. The study has been separated in three steps. The first one aimed to study both neutral and cationic molecules derived from imidazolic ring to understand the difference between cations that can form ILs and their precursors. Raman spectroscopy gave information about the changes in the vibrational modes with the substitutions. The results show that the intensity of modes from the ring decreases with the substitutions, while the contribution of -CH modes increases. In accordance with this are the results obtained from theoretical calculation of Mulliken charge, used as an auxiliary technique. The second step consisted in the study of pure ILs, analyzing both cation and anion effects. The carbonic chain plays a major role in Raman spectra, exhibiting bands attributed to different conformers. These bands become more abundant and less intense when the chain length increases. The anions have been studied in both ILs and inorganic salts, being observed very similar spectra for all the ILs but different ones for the inorganic salts. These results have been confirmed by XANES (X-ray absorption near edge structure) spectroscopy, which makes possible to probe the electronic structure of different atoms. After the analysis of both cation and anion, it was possible to better understand the ion pair formation in ILs, focusing in hydrogen bonds in the carbonic chain, since the Coulombic interaction is too weak. For ILs with hydrogen in carbon 2, it could be observed that bromide anion forms a stronger ion pair when compared to PF6- and TFSI-, less coordinating anions. The addition of methyl group in carbon 2 modifies this behavior, and even bromide does not form the strong ion pair. At last, the third step focused in the better understanding of binary systems containing ILs and a molecular solvent, dimethylformamide (DMFA), used also as probe since the shift of the band attributed to C=O group was used in this study. In a first stage it has been studied equimolar solutions of ILs and DMFA, in which it has been observed the organization of ILs in the mixture, and the contribution of both cation and anion. The second stage was dedicated to the understanding of these mixtures with different molar fraction of ILs and DMFA, for which some ILs have been selected. For low concentration of ILs, their behavior was similar to molecular solvents, but when the concentration of IL was increased, an anomalous behavior in the shift of C=O band has been observed, which can be attributed to the ionic character of these systems.
 
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Publishing Date
2011-01-10
 
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