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Hydrophobicity/Hydrophilicity of 1-Butyl-2,3-dimethyl and 1-Ethyl-3-methylimodazolium Ions: Toward Characterization of Room Temperature Ionic Liquids

TitleHydrophobicity/Hydrophilicity of 1-Butyl-2,3-dimethyl and 1-Ethyl-3-methylimodazolium Ions: Toward Characterization of Room Temperature Ionic Liquids
Publication TypeJournal Article
Year of Publication2009
AuthorsKato, H, Miki, K, Mukai, T, Nishikawa, K, Koga, Y
JournalJournal of Physical Chemistry B
Volume113
Pagination14754-14760
Date PublishedNov
Type of ArticleArticle
ISBN Number1520-6106
Keywords1-BUTYL-3-METHYLIMIDAZOLIUM BROMIDE, AGGREGATION BEHAVIOR, ALKYL CHAIN-LENGTH, APPROACH, AQUEOUS-SOLUTIONS, HOFMEISTER SERIES, MIXING SCHEMES, MOLECULAR-ORGANIZATION, partial molar enthalpy, PHYSICOCHEMICAL PROPERTIES, THERMODYNAMIC
Abstract

We continue to experimentally characterize the constituent ions of room temperature ionic liquids in terms of their interactions with H2O. By using the so-called 1-propanol probing methodology, we experimentally index the relative hydrophobicity/hydrophilicity of a test ion. In this paper, we examine 1-butyl-2,3 dimethylimidazolium (abbreviated as [C(4)C(1)mim](+)) and 1-ethyl-3-methylimidazolium ([C(2)mim](+)). We found that [C(4)C(1)mim](+) dissociates completely in dilute aqueous solution less than 0.006 mol fraction, and hence, its hydrophobicity/hydrophilicity could be determined. The results indicate that [C(4)C(1)mim](+) is highly amphiphilic with much stronger hydrophobicity and hydrophilicity than normal ions. Our earlier similar studies indicated the same conclusion for such typical constituent ions as 1-butyl-3-methylimidazolium ([C(4)mim](+)) PF6-, CF3SO3-, and N(SO2CF3)(2)(-). Hence, we suggest that the constituent ions of room temperature ionic liquids that we have studied so far are all amphiphiles with much stronger hydrophobicity and hydrophilicity than normal ions. We found, furthermore, that the hydrophobicity and hydrophilicity of [C(4)C(1)mim](+) are stronger than those for [C(4)mim](+). A possible reason for higher hydrpohilicity is discussed in terms of strong acidic character of H on the C(2) of the imidazolium ring, which tends to attract the delocalized positive charge toward itself oil forming a hydrogen bond to H2O. On replacing it with CH3 in [C(4)C(1)mim](+), the lack of acidic H enhances the positive charge in the vicinity of N-C-N in the ring that interacts with the surrounding H2O strongly to an induced dipole of O of the H2O. For [C(2)mim](+), we found it does not dissociate completely, even in dilute aqueous solution, and hence, we could not characterize it within the present methodology.

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