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Title: Solute-induced dissolution of hydrophobic ionic liquids in water.

Abstract

No abstract prepared.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
928636
Report Number(s):
ANL/CHM/JA-57353
Journal ID: ISSN 0039-9140; TLNTA2; TRN: US200812%%310
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Talanta; Journal Volume: 72; Journal Issue: 1 ; Apr. 15, 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IONIC CRYSTALS; LIQUID CRYSTALS; DISSOLUTION; WATER; SOLUTES; CATALYTIC EFFECTS

Citation Formats

Rickert, P. G., Stepinski, D. C., Rausch, D. J., Bergeron, R. M., Jakab, S., Dietz, M. L., Chemistry, BP Naperville, and Ecole Nationale Superieure de Chimie de Paris. Solute-induced dissolution of hydrophobic ionic liquids in water.. United States: N. p., 2007. Web. doi:10.1016/j.talanta.2006.10.033.
Rickert, P. G., Stepinski, D. C., Rausch, D. J., Bergeron, R. M., Jakab, S., Dietz, M. L., Chemistry, BP Naperville, & Ecole Nationale Superieure de Chimie de Paris. Solute-induced dissolution of hydrophobic ionic liquids in water.. United States. doi:10.1016/j.talanta.2006.10.033.
Rickert, P. G., Stepinski, D. C., Rausch, D. J., Bergeron, R. M., Jakab, S., Dietz, M. L., Chemistry, BP Naperville, and Ecole Nationale Superieure de Chimie de Paris. Sun . "Solute-induced dissolution of hydrophobic ionic liquids in water.". United States. doi:10.1016/j.talanta.2006.10.033.
@article{osti_928636,
title = {Solute-induced dissolution of hydrophobic ionic liquids in water.},
author = {Rickert, P. G. and Stepinski, D. C. and Rausch, D. J. and Bergeron, R. M. and Jakab, S. and Dietz, M. L. and Chemistry and BP Naperville and Ecole Nationale Superieure de Chimie de Paris},
abstractNote = {No abstract prepared.},
doi = {10.1016/j.talanta.2006.10.033},
journal = {Talanta},
number = 1 ; Apr. 15, 2007,
volume = 72,
place = {United States},
year = {Sun Apr 15 00:00:00 EDT 2007},
month = {Sun Apr 15 00:00:00 EDT 2007}
}
  • Radical chemistry initiated by one-electron reduction of 1-methyl-3-alkylimidazolium cations in the corresponding ionic liquids (ILs) is examined. The reaction scheme is examined in light of the recent experimental data on photo-, radiation-, and electrochemically induced degradation of the practically important hydrophobic alkylimidazolium ILs. It is suggested that the primary species leading to the formation of the oligomers and acidification of the IL is a {sigma}{sigma}* dimer radical cation that loses a proton, yielding a neutral radical whose subsequent reactions produce C(2)-C(2) linked oligomers, both neutral and charged. The neutral oligomers (up to the tetramer) account for the features observed inmore » the NMR spectra of cathodic liquid generated in electrolytic breakdown of the IL solvent. In photolysis and radiolysis, these neutral species and/or their radical precursors are oxidized by radical (ions) derived from the counteranions, and only charged dimers are observed. The dication dimers account for the features observed in the mass spectra of irradiated ILs. The products of these ion radical and radical reactions closely resemble those generated via carbene chemistry, without the formation of the carbene via the deprotonation of the parent cation. As the loss of 2-protons increases the proticity of the irradiated IL, it interferes with the extraction of metal ions by ionophore solutes, while the formation of the oligomers modifies solvent properties. Thus, the peculiarities of radical chemistry in the alkylimidazolium ILs have significant import for their practical applications.« less
  • Extraction of dilute metal ions from water was performed near room temperature with a variety of ionic liquids. Distribution coefficients are reported for fourteen metal ions extracted with ionic liquids containing cations 1-octyl-4-methylpyridinium [4MOPYR]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPYRRO]{sup +} or 1-methyl-1-octylpiperidinium [MOPIP]{sup +}, and anions tetrafluoroborate [BF{sub 4}]{sup +}, trifluoromethyl sulfonate [TfO]{sup +} or nonafluorobutyl sulfonate [NfO]{sup +}. Ionic liquids containing octylpyridinium cations are very good for extracting mercury ions. However, other metal ions were not significantly extracted by any of these ionic liquids. Extractions were also performed with four new task-specific ionic liquids. Such liquids containing a disulfide functional groupmore » are efficient and selective for mercury and copper, whereas those containing a nitrile functional group are efficient and selective for silver and palladium.« less
  • Using the modified versions of the scaled particle theory amended by Stillinger, the influence of nonpolar solute size on its thermodynamic parameters of transfer from gas to water or from light to heavy water has been investigated. In the first case it is found that the process is dominated by an entropy contribution at small solute size and an enthalpy contribution at larger size. In the second process the increase in solute size also results in a change in the sign of the free energy and enthalpy of transfer, which is supported by experimental data on bulky solutes, such asmore » adamantanemethanol or sodium adamantanecarboxylate.« less
  • The influence of water on the observed gas-phase population of negative ions in electrospray mass spectrometry was studied for the undiluted ionic liquid 1,3-butyl-methyl-imidazolium hexafluorophosphate (BMIMPF6 ). During the electrospray process, electrolytic reduction of water enhances the production of tetrafluorophosphate (F4PO), which undergoes further reactions to produce difluorophosphate (F2PO2 ) anions. These anions are observed in addition to the pre-existing hexafluorophosphate anion. The apparent substitution of two fluorine atoms with one oxygen is attributed to a series of reactions initiated by hydrolysis of hexafluorophosphate. This hydrolysis reaction was enhanced by the addition of hydroxide, formed via the hydrolysis of watermore » or through the addition of ammonium hydroxide. The formation of FxPOy was studied as a function of the electrospray current and solution flow rate. The mass spectral response shows a quantitative logarithmic relationship between FxPOy signal intensities (adjusted for mole equivalents of H2O required) and the amount of water present, against which the water content could be rapidly assessed. Results were found to be comparable to Karl Fischer titration data« less
  • Different inner-sphere coordination environments are observed for the uranyl nitrate complexes formed with octyl-phenyl-N,N-diisobutylcarbamoylmethylphosphine oxide and tributyl phosphate in dodecane and in the hydrophobic ionic liquids (ILs) [C{sub 4}mim][PF{sub 6}] and [C{sub 8}mim][N(SO{sub 2}CF{sub 3}){sub 2}]. Qualitative differences in the coordination environment of the extracted uranyl species are implied by changes in peak intensity patterns and locations for uranyl UV-visible spectral bands when the solvent is changed. EXAFS data for uranyl complexes in dodecane solutions is consistent with hexagonal bipyramidal coordination and the existence of UO{sub 2}(NO{sub 3}){sub 2}(CMPO){sub 2}. In contrast, the complexes formed when uranyl is transferred frommore » aqueous nitric acid solutions into the ILs exhibit an average equatorial coordination number of approximately 4.5. Liquid/liquid extraction results for uranyl in both ILs indicate a net stoichiometry of UO{sub 2}(NO{sub 3})(CMPO){sup +}. The concentration of the IL cation in the aqueous phase increases in proportion to the amount of UO{sub 2}(NO{sub 3})(CMPO){sup +} in the IL phase, supporting a predominantly cation exchange mechanism for partitioning in the IL systems.« less