Aggregation Behavior of Ionic Liquids in Aqueous Solutions:  Effect of Alkyl Chain Length, Cations, and Anions

Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H...

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Published inThe journal of physical chemistry. B Vol. 111; no. 27; pp. 7843 - 7851
Main Authors Singh, Tejwant, Kumar, Arvind
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 12.07.2007
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Abstract Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation Δ of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.
AbstractList Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.
Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation Δ of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.
Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], N-butyl-3-methylpyridinium chloride [C4mpy][Cl], in aqueous solution has been investigated through 1H nuclear magnetic resonance (NMR) and steady-state fluorescence spectroscopy. Aggregation properties were determined by application of mass action theory to the concentration dependence of 1H NMR chemical shifts. Aggregation properties showed fairly good agreement with the previously reported results obtained from small angle neutron scattering, conductivity, and surface tension measurements. A detailed analysis of chemical shifts of water and various protons in ILs has been employed to probe the aggregate structure. Fluorescence spectroscopy provided important information about the critical aggregation concentration (cac) and the microenvironment of the aggregates. We could also observe a break point quite consistent with that of 1H NMR and fluorescence spectroscopy at cac from the concentration dependence of refractive index measurements. Standard free energies of aggregation DeltaGom of various ILs derived using the refractive index/concentration profiles were found comparable to those of classical ionic surfactants.
Author Kumar, Arvind
Singh, Tejwant
Author_xml – sequence: 1
  givenname: Tejwant
  surname: Singh
  fullname: Singh, Tejwant
– sequence: 2
  givenname: Arvind
  surname: Kumar
  fullname: Kumar, Arvind
BackLink https://www.ncbi.nlm.nih.gov/pubmed/17571879$$D View this record in MEDLINE/PubMed
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Snippet Self aggregation of the ionic liquids, 1-butyl-3-methylimidazolium chloride [C4mim][Cl], 3-methyl-1-octylimidazolium chloride [C8mim][Cl],...
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Title Aggregation Behavior of Ionic Liquids in Aqueous Solutions:  Effect of Alkyl Chain Length, Cations, and Anions
URI http://dx.doi.org/10.1021/jp0726889
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