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Ionic Liquids as Novel Ionic Liquids as Novel Solvents Solvents
for Extractionfor Extraction
Inna E PopóvaInna E Popóva
Number of PublicationsNumber of Publications
Determined using SciFinder
What are Ionic Liquids?What are Ionic Liquids?
[PRxH4-x]+[NRxH4-x]
+NN
R RN
R
[AlCl4]- [BF4]
- [PF6]-
Common Cations
Common anions
What are their properties?What are their properties?
Dissolve most organic and Dissolve most organic and inorganic compounds inorganic compounds
High thermal stability High thermal stability No measurable vapor pressure No measurable vapor pressure Non-flammableNon-flammable Liquid up to 300ºCLiquid up to 300ºC
Welton, T. Chem Rev. 1999, 99, 2071-2083.
What are their applications?What are their applications?
As solvent for syntheses As solvent for syntheses As catalysts As catalysts As electrolytesAs electrolytes In extraction and separation In extraction and separation
technologiestechnologies
Welton, T. Chem Rev. 1999, 99, 2071-2083.
Extraction Using Crown Extraction Using Crown EthersEthers
organic phase
ligand
D(SrD(Sr2+2+)) D(CsD(Cs++))
nn--octanoloctanol
[C[C44mim]mim][PF[PF66]]
nn-octanol-octanol[C[C44mim]mim]
[PF[PF66]]
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
Visser, A.; Swatloski, R.; Reichert, W.; Griffin, S.; Rogers, R. Ind. Eng. Chem. Res. 2000, 39, 3596-3604.
0.030.03 1·101·10-3-3~ 1~ 1 0.0.11
3.33.311
15.815.8
5·105·10-2-2
0.10.1
2244
101055
1010
9292
Kumar, A.; Mohapatra, P.; Pathak, P.; Manchanda, V. Talanta 1997, 45, 387-395.
Organic phase
Aqueous phase
An ion pair mechanism A cation-exchange mechanism
Aqueous phase
IL phase
Extraction UsingExtraction Using Mono-Mono-aza Crown Ethersaza Crown Ethers
Luo, H.; Dai, Sh.; Bonnese, P. Anal. Chem. 2004, 76, 2773-2779.
LigandLigand D(SrD(Sr2+2+)) D(CsD(Cs2+2+))
1070010700 935935
84308430 10701070
O
O
O
O
O
O
O
N
O
O
O
O
H17C8
Extraction Using Extraction Using CalixarenesCalixarenes
http://www.people.virginia.edu/~cdt9f/homepg.htm accessed in October 2004
Extraction Using Extraction Using CalixarenesCalixarenes
Shimojo, K.; Goto, M. Chem. Lett. 2004, 33, 320-321.
Extraction Using Extraction Using Crown-Calixarene Crown-Calixarene
CompoundsCompounds
D(CsD(Cs2+2+)) D(KD(K++)) D(NaD(Na++)) D(SrD(Sr2+2+))
CsCs++ + K + K++ + Na + Na++ 371371 7.007.00 ~ 0~ 0
CsCs++ + K + K++ 228228 8.088.08
CsCs++ + K + K++ + Sr + Sr2+2+ 576576 8.398.39 ~ 0~ 0
Luo, H.; Dai, Sh.; Bonnesen, P.; Buchanan, A.; Holbrey, J.; Bridges, N.; Rogers, R. Anal. Chem. 2004, 76, 3078-3083.
Extraction Using DithizoneExtraction Using Dithizone
Wei, G.; Yang, Z.; Chen, C. Anal. Chim. Acta. 2003, 488, 183–192.
Cd2+ Ag+ Cu2+ Pb2+ Zn2+
N
NHNH
N
S
Me(I)
N
NNH
N
S Me(II)
N
NNH
N
S
N
NNH
N
S
Extraction Using Extraction Using DithizoneDithizone
Wei, G.; Yang, Z.; Chen, C. Anal. Chim. Acta. 2003, 488, 183–192.
Cd2+ Ag+ Cu2+ Pb2+ ●Zn2+
Extraction Using Task Extraction Using Task Specific ILsSpecific ILs
Visser, A.; Swatloski, R.; Reichert, W.; Mayton, R.; Sheff, S.; Wierzbicki, A.;
Davis, J.; Rogers, R. Env. Sci. Technol. 2002, 36, 2523-2529.
N NCH3
S
CH3
NH
NH
S
NN
CH3
CH3
N N
CH3 NH
NH
O
CH3NH
NH
S
CH3
Hg N N
CH3
CH3
NH
NH
S
CH3
NN
CH3
CH3
Extraction of Phenolic Extraction of Phenolic Compounds ICompounds I
OH
OH
OH OH
OH
O
phenol
tyrosol p-hydroxybenzoic acid
Vidal, S.; Correia, M.; Marques, M; Ismael, R; Reis, T. Sep. Sci. Technol. 2004, 39, 2155-2169.
Extraction efficiency, %Extraction efficiency, %
1-Octanol1-Octanol 9595 6868 9191
[C[C88mim][BFmim][BF44]]
9090 7979 9393
Extraction of Phenolic Extraction of Phenolic Compounds IICompounds II
Cl
OH
Cl
OH
Cl
Cl
OH
Cl
Cl
Cl
OH
Cl
Cl
Cl
Bekou, E.; Dionysiou, D.; Qian, R.; Botsaris, G. ACS Symposium Series. 2003, 856, 544-560.
●
Extraction of Amino Extraction of Amino AcidsAcids
Trp Gly
AlaLeu
O
NH3+
CH3
CH3
O-
O
NH3+
NH
O-
O
NH3+
CH3O
-
O
NH3+
O-
Extraction of Amino Extraction of Amino AcidsAcids
Smirnova, S.; Torocheshnikova, I.; Formanovsky, A.; Pletnev, I.
Analytical and Bioanalytical Chemistry 2004, 378, 1369-1375.
Amino AcidAmino Acid DDRecovery, Recovery,
%%
TrpTrp 7676 96±396±3
GlyGly 5858 95±395±3
LeuLeu 4040 93±393±3
AlaAla 3232 92±392±3
ConclusionsConclusions
ILs are good replacement for ILs are good replacement for conventional solventsconventional solvents
ILs provide higher selectivity and ILs provide higher selectivity and effectivity for extraction of charged effectivity for extraction of charged species (metal ions, zwitterions)species (metal ions, zwitterions)
ILs can be potentially used for organic ILs can be potentially used for organic compounds extractioncompounds extraction
Future worksFuture works
Improvement ofthe design of
a chelating agent
Improvementof the
design of ILs
Combination of a chelating agent
with ILs
Calixarenes,Calixarene-Crown
Compounds
Synthesis of
new ILs
TSILs
