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      Mechanisms ruling the partition of solutes in ionic-liquid-based aqueous biphasic systems – the multiple effects of ionic liquids

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          Abstract

          The partition of solutes in ionic-liquid-based aqueous biphasic systems is due a multiple effect resulting from both solute–solvent and specific solute–ionic-liquid interactions.

          Abstract

          In the past decade, the remarkable potential of ionic-liquid-based aqueous biphasic systems (IL-based ABSs) to extract and purify a large range of valued-added biocompounds has been demonstrated. However, the translation of lab-scale experiments to an industrial scale has been precluded by a poor understanding of the molecular-level mechanisms ruling the separation or partition of target compounds between the coexisting phases. To overcome this limitation, we carried out a systematic evaluation of specific interactions, induced by ILs and several salts used as phase-forming components, and their impact on the partition of several solutes in IL-based ABSs. To this end, the physicochemical characterization of ABSs composed of imidazolium-based ILs, three salts (Na 2SO 4, K 2CO 3 and K 3C 6H 5O 7) and water was performed. The ability of the coexisting phases to participate in different solute–solvent interactions (where “solvent” corresponds to each ABS phase) was estimated based on the Gibbs free energy of transfer of a methylene group between the phases in equilibrium, Δ G(CH 2), and on the Kamlet–Taft parameters – dipolarity/polarizability (π*), hydrogen-bonding donor acidity ( α) and hydrogen-bonding acceptor basicity ( β) – of the coexisting phases. Relationships between the partition coefficients, the phase properties expressed as Kamlet–Taft parameters and COSMO-RS descriptors were established, highlighting the ability of ILs to establish specific interactions with given solutes. The assembled results clearly support the idea that the partition of solutes in IL-based ABSs is due to multiple effects resulting from both global solute–solvent and specific solute–IL interactions. Solute–IL specific interactions are often dominant in IL-based ABSs, explaining the higher partition coefficients, extraction efficiencies and selectivities observed with these systems when compared to more traditional ones majorly composed of polymers.

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          Most cited references 48

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          Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena

           Andreas Klamt (1995)
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            Ionic liquids: solvent properties and organic reactivity

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              Controlling the aqueous miscibility of ionic liquids: aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle, metathesis, and separations.

              Hydrophilic ionic liquids can be salted-out and concentrated from aqueous solution upon addition of kosmotropic salts forming aqueous biphasic systems as illustrated by the phase behavior of mixtures of 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) and K3PO4.
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                Author and article information

                Journal
                PPCPFQ
                Physical Chemistry Chemical Physics
                Phys. Chem. Chem. Phys.
                Royal Society of Chemistry (RSC)
                1463-9076
                1463-9084
                2018
                2018
                : 20
                : 13
                : 8411-8422
                Affiliations
                [1 ]CICECO – Aveiro Institute of Materials
                [2 ]Department of Chemistry
                [3 ]University of Aveiro
                [4 ]3810-193 Aveiro
                [5 ]Portugal
                Article
                10.1039/C8CP00383A
                6161819
                29542784
                © 2018
                Product
                Self URI (article page): http://xlink.rsc.org/?DOI=C8CP00383A

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