Abstract
An overview on specific phenomena in extraction of carboxylic acids with hydrophobic ionic liquids (ILs) based on results of new measurements with selected phosphonium, ammonium and imidazolium ILs and published data is presented. Formation of IL – acid hydrated complexes with multiple molecules of organic acid per one IL ion pair was observed. The distribution coefficient of carboxylic acids and water content in ILs strongly decreases with the increasing acid concentration. Dependence of water content in the solvent passes through a minimum at loading of IL with butyric acid of about 3. Two extraction mechanisms are involved: competitive extraction of acid and water with the release of water from the solvent and co-extraction of water with acid depending on the IL concentration. A strong synergistic effect was observed between the cation and anion of ILs enhancing their extractive properties compared to IL precursors. A new extraction model suggests the formation of water bridges and polar nano-channels which is in agreement with the molecular modelling results. ILs are nano-segregated liquids with a structure sensitive to the content of molecular compounds. Water and carboxylic acids accumulate in polar domains and dodecane in non-polar domains modifying the IL structure and decreasing the solvent phase viscosity. The hypothesis of hopping mechanism in polar channels for acid molecules transport between acid chains at IL binding sites is suggested.
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Abbreviations
- c :
-
Molar concentration of acid if not other component is specified by lower indices (kmol m−3)
- \(c^{ * }\) :
-
Molar concentration of acid in equilibrium (kmol m−3)
- \(c_{\text{aF}}^{ * }\) :
-
Analytical molar concentration of acid in equilibrium (kmol m−3)
- \(c_{\text{Fo}}\) :
-
Initial molar concentration of acid in the feed (kmol m−3)
- D a :
-
Distribution coefficient of acid
- K p :
-
Equilibrium constant characterizing the stability of the acid−acid bond in (p, 1) complex between (p−1) and p-th acids (m3 kmol−1)
- w :
-
Mass fraction
- x :
-
Molar fraction
- \(X_{\text{IL}}\) :
-
Relative molar fraction of IL based on the content of IL and dodecane \(X_{\text{IL}} = x_{\text{IL}} /(x_{\text{IL}} + x_{\text{dodecane}} )\)
- z :
-
Loading of IL by acid in equilibrium, \(z = c_{\text{S}} /c_{\text{S, IL}}\)
- \(z_{{{\text{H}}_{2} {\text{O}}}}\) :
-
Loading of IL by water in equilibrium, \(z_{{{\text{H}}_{2} {\text{O}}}} = c_{{{\text{S, H}}_{ 2} {\text{O}}}} /c_{\text{S, IL}}\)
- η :
-
Dynamic viscosity, Pas
- F:
-
Feed (aqueous) phase
- H2O:
-
Water
- IL:
-
Ionic liquid
- S:
-
Solvent phase
- AH:
-
Undissociated organic acid
- BA:
-
Butyric acid
- BAH:
-
Undissociated butyric acid
- (BAH) p (IL):
-
(p, 1) Complex of BA with IL ion pair
- DLS:
-
Dynamic light scattering
- IL:
-
Ionic liquid (IL ion pair)
- LA:
-
Lactic acid
- LAH:
-
Undissociated lactic acid
- SIR:
-
Solvent impregnated resin
- SPD:
-
Short path distillation
- TOA:
-
Trioctylamine
- C12 :
-
Dodecane
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Acknowledgements
Supports of the Slovak Grant Agencies under projects No. VEGA 1/0757/14 and APVV -15-0494 are acknowledged. Authors are grateful to Cytec (CDN) and to Cognis (DE) for kindly providing samples of ionic liquids Cyphos and extractant Cyanex 272, and Aliquat 336, respectively.
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Schlosser, Š., Marták, J. & Blahušiak, M. Specific phenomena in carboxylic acids extraction by selected types of hydrophobic ionic liquids. Chem. Pap. 72, 567–584 (2018). https://doi.org/10.1007/s11696-017-0365-7
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DOI: https://doi.org/10.1007/s11696-017-0365-7