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Mechanism of ionic-liquid-based acidic aqueous biphasic system formation1

Schaeffer, Nicolas et al.

Physical chemistry chemical physics. Volume 20:Issue 15 (2018); pp 9838-9846 -- Royal Society of Chemistry

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  • Title:
    Mechanism of ionic-liquid-based acidic aqueous biphasic system formation1
  • Author: Schaeffer, Nicolas;
    Passos, Helena;
    Gras, Matthieu;
    Mogilireddy, Vijetha;
    Leal, João P.;
    Pérez-Sánchez, Germán;
    Gomes, José R. B.;
    Billard, Isabelle;
    Papaiconomou, Nicolas;
    Coutinho, João A. P.
  • Found In: Physical chemistry chemical physics. Volume 20:Issue 15 (2018); pp 9838-9846
  • Journal Title: Physical chemistry chemical physics
  • Subjects: Chemistry, Physical and theoretical--Periodicals; Dewey: 541.3
  • Rights: legaldeposit
  • Publication Details: Royal Society of Chemistry
  • Abstract: Abstract :

    This work represents a major contribution to the understanding of ionic liquid-based acidic aqueous biphasic system formation and application.

    Abstract :

    Ionic-liquid-based acidic aqueous biphasic systems (IL-based AcABS) represent a promising alternative to the solvent extraction process for the recovery of critical metals, in which the substitution of the inorganic salt by an acid allows for a 'one-pot' approach to the leaching and separation of metals. However, a more fundamental understanding of AcABS formation remains wanting. In this work, the formation mechanisms of AcABS are elucidated through a comparison with traditional aqueous biphasic systems (ABS). A large screening of AcABS formation with a wide range of IL identifies the charge shielding of the cation as the primary structural driver for the applicability of an IL in AcABS. Through a systematic study of tributyltetradecylphosphonium chloride ([P44414]Cl) with various chloride salts and acids, we observed the first significant deviation to the cationic Hofmeister series reported for IL-based ABS. Furthermore, the weaker than expected salting-out ability of H3O + compared to Na + is attributed to the greater interaction of H3O + with the [P44414] + micelle surface. Finally, the remarkable thermomorphic properties of [P44414]Cl based systems are investigated with a significant increase in the biphasic region induced by the increase in the temperature from 298 K to 323 K. These finding allows for the extension of ABS to new acidic systems and highlights their versatility and tunability.


  • Identifier: System Number: LDEAvdc_100059252261.0x000001; Journal ISSN: 1463-9076; 10.1039/c8cp00937f
  • Publication Date: 2018
  • Physical Description: Electronic
  • Shelfmark(s): ELD Digital store

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