1H NMR and Molecular Dynamics Evidence for an Unexpected Interaction on the Origin of Salting-In/Salting-Out Phenomena

• Type: Article in International Scientific Journal
• Date: 2010

Authors

Mara G. Freire (Author) Other; Catarina M. S. S. Neves (Author) Other; Artur M. S. Silva (Author) Other; Luís M. N. B. F. Santos (Author) FCUP; Isabel M. Marrucho (Author) Other; Luís P. N. Rebelo (Author) Other; Jindal K. Shah (Author) Other; Edward J. Maginn (Author) Other; João A. P. Coutinho (Author) Other

Journal

Title: Journal of Physical Chemistry B

Vol. 114 No. 5

Pages: 2004-2014

ISSN: 1520-6106

Publisher: American Chemical Society

Indexing

Scopus

Scientific classification

FOS: Engineering and technology > Chemical engineering

CORDIS: Physical sciences > Chemistry > Physical chemistry ; Physical sciences > Chemistry > Analytical chemistry > Spectrochemistry

Other information

Abstract (EN): By employing 1H NMR spectroscopy and molecular simulations, we provide an explanation for recent observations that the aqueous solubilities of ionic liquids exhibit salting-out to salting-in regimes upon addition of distinct inorganic salt ions. Using a typical ionic liquid [1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide], we observed the existence of preferential specific interactions between the low electrical charge density (“apolar moiety”) parts of the ionic liquid cation and the inorganic salts. These a priori unexpected interactions become increasingly favorable as one moves from salting-out to salting-in effects. More specifically, this interpretation is validated by distinct aqueous solution 1H NMR data shifts in the ionic liquid cation upon inorganic salt addition. These shifts, which are well noted in the terminal and preterminal hydrogens of the alkyl chain appended to the imidazolium ring, correlate quantitatively with solubility data, both for cases where the nature of inorganic salt is changed, at constant concentration, and for those where the concentration of a given inorganic salt is varied. Molecular simulations have also been performed permitting us to garner a broader picture of the underlying mechanism and structure of this complex solvation phenomenon. These findings can now be profitably used to anticipate solution behavior upon inorganic salt addition well beyond the specificity of the ionic liquid solutions, i.e., for a diversity of distinct solutes differing in chemical nature.

Language: English

Type (Professor's evaluation): Scientific