Abstract
Liquid–liquid equilibrium data on butyric acid (BA) extraction by new ionic liquid (IL) tetradecyl(trihexyl)phosphonium neodecanoate ([C14C6C6C6P][NDec]) are presented and correlated using a model developed earlier. Extraction performance of the new IL is comparable with that of previously tested phosphonium ILs with decanoate and phosphinate anions. High loading of IL with BA of more than 12 BA molecules per one IL ion pair was achieved at aqueous BA concentration of 1.2 mol dm−3. The overall extraction mechanism includes competitive extraction of BA and water, and coextraction of BA with water. Both these sub-mechanisms act simultaneously, the first one dominates below IL loading by acid of 2 and the second one above this value. Dynamic viscosity of water saturated [C14C6C6C6P][NDec] is slightly higher compared to a similar IL with decanoate anion [C14C6C6C6P][Dec] (104 and 96 mPa s). However, at 298 K dried [C14C6C6C6P][Dec] is solid, while [C14C6C6C6P][NDec] is liquid even below 253 K which is a great advantage. Viscosity of equilibrium organic phases shows a maximum at IL loading by BA of about 1.6 which corresponds to the minimal solute (BA + water) content and maximal molar fraction of IL due to water release from the solvent.
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Abbreviations
- A :
-
Empirical parameter in Eq. 14
- B :
-
Empirical parameter in Eq. 14
- C :
-
Empirical parameter in Eq. 14
- c 0 :
-
Concentration of water saturated IL in the organic phase in equilibrium (mol dm−3)
- c aF :
-
Total (analytical) concentration of BA in the aqueous phase in equilibrium (mol dm−3)
- c d :
-
Concentration of BA dimer in the organic phase in equilibrium (mol dm−3)
- c F :
-
Concentration of undissociated BA in the aqueous phase in equilibrium (Eq. 6) (mol dm−3)
- c F,ef :
-
Effective BA concentration in the aqueous phase in equilibrium (Eq. 3) (mol dm−3)
- c I :
-
Total concentration of IL in the organic phase in equilibrium (mol dm−3)
- c m :
-
Concentration of BA monomer in the organic phase in equilibrium (mol dm−3)
- c p :
-
Concentration of complex (p, 1) in the organic phase in equilibrium (mol dm−3)
- c S,phys :
-
BA concentration in the organic phase in equilibrium for experiments with IL diluted by dodecane (mol dm−3)
- c S,phys,Dod :
-
BA concentration in the organic phase in equilibrium for experiments with pure dodecane (mol dm−3)
- c S,react :
-
Concentration of reactively extracted BA by IL in the organic phase in equilibrium (mol dm−3)
- c W,S,comp :
-
Concentration of water competitively extracted by IL in the organic phase in equilibrium (mol dm−3)
- D a :
-
Distribution coefficient of BA related to caF for experiments with solvents containing IL
- D a,phys,Dod :
-
Distribution coefficient of BA related to caF for experiments with pure dodecane
- D phys,Dod :
-
Distribution coefficient of BA related to cF for experiments with pure dodecane
- k BA,int :
-
BA–BA interaction parameter in the aqueous phase (dm3 mol−1)
- K d :
-
BA dimerization constant (Eq. 2) (dm3 mol−1)
- K m :
-
Extraction constant of BA monomer (Eq. 1)
- K p :
-
Stability constant of complex (p,1) (Eq. 9) (dm3 mol−1)
- k p :
-
Stoichiometric coefficient of competitively extracted water in complex
(p,1)
- k PA,int :
-
PA–PA interaction parameter in the aqueous phase (dm3 mol−1)
- l 0, p :
-
Stoichiometric coefficient of water in water saturated IL
- \(l_{{w_{{{\text{Io}}}} ,p}}\) :
-
Stoichiometric coefficient of water coextracted with BA in complex (p,1) for solvent with given wIo (Eq. 8)
- M BA :
-
Molar mass of BA, 88.11 g mol−1
- m BAo :
-
Total mass of BA added to the liquid–liquid equilibrium experiment (g)
- m F :
-
Aqueous phase mass in equilibrium (g)
- m S :
-
Organic phase mass in equilibrium (g)
- m So :
-
Mass of dry organic solvent added to the liquid–liquid equilibrium experiment (g)
- p :
-
Number of BA molecules in BA–IL complex (p,1)
- pHF :
-
PH in the aqueous phase in equilibrium
- R 2 :
-
Coefficient of determination
- SD:
-
Standard deviation
- T :
-
Temperature (K)
- V BA,phys :
-
Volume of physically extracted acid in the organic phase in equilibrium for experiments with IL diluted by dodecane (mol dm−3)
- V Dod :
-
Volume of dodecane in the organic phase in equilibrium for experiments with IL diluted by dodecane (mol dm−3)
- V S,phys :
-
Summary volume of dodecane and physically extracted acid in the organic phase in equilibrium for experiments with IL diluted by dodecane (mol dm−3)
- w BA,F :
-
Mass fraction of BA in the aqueous phase in equilibrium
- w BA,S :
-
Mass fraction of BA in the organic phase in equilibrium
- w Io :
-
Mass fraction of IL in dry organic solvent before extraction
- w W :
-
Mass fraction of water
- z BA :
-
Loading of IL by reactively extracted BA
- z W,coext :
-
Loading of IL by water coextracted with BA
- \(z_{{{\tt W,}w_{{\rm Io}}}}\) :
-
Total loading of IL by water for solvent with given wIo
- Δ:
-
Material balance of liquid–liquid equilibrium experiment
- δ :
-
Fitting parameter for calculation of zW, coext (Eq. 16)
- η S :
-
Viscosity of the organic phase in equilibrium, mPa.s
- ρ BA :
-
Density of BA (g dm−3)
- ρ D :
-
Density of dodecane (g dm−3)
- ρ S :
-
Density of organic phase in equilibrium (g dm−3)
- BA:
-
Butyric acid
- [C14C6C6C6P][NDec]:
-
Tetradecyl(trihexyl)phosphonium neodecanoate
- IL:
-
Ionic liquid
- (p,1):
-
Complex containing p molecules of BA and one ion pair of IL
- ws:
-
Water saturated
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Support of the Slovak grant agency APVV, Project No. 15-0494 is acknowledged.
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Marták, J., Liptaj, T., Polakovič, M. et al. New phosphonium ionic liquid with neodecanoate anion as butyric acid extractant. Chem. Pap. 75, 3965–3977 (2021). https://doi.org/10.1007/s11696-021-01607-w
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DOI: https://doi.org/10.1007/s11696-021-01607-w