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Cited by 1,441Ionic liquids properties and applicationsSpectroscopy and Quantum Chemical StudiesN-Heterocyclic Carbenes in Organic and Inorganic Chemistry

Molecular states of water in room temperature ionic liquidsElectronic Supplementary Information available. See http://www.rsc.org/suppdata/cp/b1/b106900d/

Cammarata, L., Kazarian, S. G., Salter, P. A., Welton, T.·2001·Physical Chemistry Chemical Physics
DOI 10.1039/b106900d
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Abstract

ATR and transmission IR spectroscopy have been used to investigate the state of water in room temperature ionic liquids (RTILs) based on the 1-alkyl-3-methylimidazolium cation with the anions: [PF6]−, [SbF6]−, [BF4]−, [ClO4]−, [CF3SO3]−, [(CF3SO2)2N]−, [NO3]− and [CF3CO2]−. It has been shown that in these RTILs water molecules absorbed from the air are present mostly in the “free” (not self-associated) state, bound via H-bonding with [PF6]−, [BF4]−, [SbF6]−, [ClO4]−, [CF3SO3]−, [(CF3SO2)2N]− with the concentrations of dissolved water in the range 0.2–1.0 mol dm−3. It has been concluded that most of the water molecules at these concentrations exist in symmetric 1 : 2 type H-bonded complexes: anion...HOH...anion. Additional evidence that the preferred sites of interaction with water molecules are the anions has been obtained from the experiments with RTILs of the 1-butyl-2,3-dimethylimidazolium and 1-butyl-2,3,4,5-tetramethylimidazolium cations. Water molecules can also form associated liquid-like formations in RTILs with anions of stronger basicity such as [NO3]− and [CF3CO2]−. When these RTILs are exposed to air the water concentrations exceed 1.0 mol dm−3. The strength of H-bonding between water molecules and anions increases in the order [PF6]− < [SbF6]− < [BF4]− < [(CF3SO2)2N]− < [ClO4]− < [CF3SO3]− < [NO3]− < [CF3CO2]−. The energies of this H-bonding were estimated from spectral shifts, with the resulting enthalpies being in the range 8–13 kJ mol−1. ATR-IR spectroscopy has also been used to study H-bonding between methanol and RTILs.

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  • For the Ionosolv and Dissolution Processes, it is important that the cellulose fraction be as free of ionic liquid as possible to avoid unwanted deactivation of the saccharification enzymes or toxicity to the fermenting microorganisms.

    “For the Ionosolv, as well as the Dissolution Process, it is important that the cellulose fraction be as free of ionic liquid as possible to avoid unwanted deactivation of the saccharification enzymes 162 or toxicity to the fermenting microorganisms.188”

    From Deconstruction of lignocellulosic biomass with ionic liquids (2013) · cites this paper as [162]

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Authors
Cammarata, L., Kazarian, S. G., Salter, P. A., & Welton, T.
Affiliations
Imperial College London (GB)
Corresponding author
Kazarian, S. G.
ORCID
Venue
Physical Chemistry Chemical Physics
Publisher
Royal Society of Chemistry (RSC)
Published
2001-11-26
Volume
3
Issue
23
Pages
5192-5200
ISSN
  • 1463-9076 (ISSN-L)
  • 1463-9084
DOI
10.1039/b106900d
OpenAlex
W1883779550
Cited by
1,441
References
27
Citations by year
2026: 15 · 2025: 18 · 2024: 34 · 2023: 31 · 2022: 41 · 2021: 50 · 2020: 58 · 2019: 64 · 2018: 58 · 2017: 57 · 2016: 80 · 2015: 91 · 2014: 88 · 2013: 95 · 2012: 93
FWCI
16.12
Type
journal article
Language
en
Open access
closed
Locations
  • Physical Chemistry Chemical Physics (publishedVersion)
  • Spiral (Imperial College London) (submittedVersion)
Funders
Engineering and Physical Sciences Research Council
Topics
  • Physical Sciences › Chemical Engineering › Catalysis › Ionic liquids properties and applications
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
  • Physical Sciences › Chemistry › Organic Chemistry › N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
Keywords
room temperature ionic liquids, water in ionic liquids, 1-alkyl-3-methylimidazolium, hydrogen bonding, anion basicity, hydrogen bond enthalpy, trifluoromethanesulfonate

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