H-1 NMR and Molecular Dynamics Evidence for an Unexpected Interaction on the Origin of Salting-In/Salting-Out Phenomena
authors Freire, MG; Neves, CMSS; Silva, AMS; Santos, LMNBF; Marrucho, IM; Rebelo, LPN; Shah, JK; Maginn, EJ; Coutinho, JAP
nationality International
journal JOURNAL OF PHYSICAL CHEMISTRY B
keywords HYDROPHOBIC IONIC LIQUIDS; AQUEOUS BIPHASIC SYSTEMS; MUTUAL SOLUBILITIES; HOFMEISTER SERIES; SELF-ASSOCIATION; WATER; PRECIPITATION; AGGREGATION; SIMULATION; BEHAVIOR
abstract By employing H-1 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 H-1 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.
publisher AMER CHEMICAL SOC
issn 1520-6106
year published 2010
volume 114
issue 5
beginning page 2004
ending page 2014
digital object identifier (doi) 10.1021/jp9095634
web of science category Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000274270100032
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journal impact factor 2.857
5 year journal impact factor 2.88
category normalized journal impact factor percentile 50.629
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