In: Handbook of Ionic Liquids ISBN 978-1-62100-349-6

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Chapter 5

THE PHYSICAL AND CHEMICAL PROPERTIES OF

IONIC LIQUIDS AND ITS APPLICATION IN
EXTRACTION

Yu Cao, Shun Yao, Xiaoming Wang, Qi Peng

∗
and Hang Song
Department of Pharmaceutical and Biological Engineering,
Sichuan University, 610065 Chengdu, China

ABBREVIATIONS
CE = capillary electrophoresis
CMC = critical micelle concentration
CMPO = octyl (phenyl)-N, N-diisobutylcarbamoylmethyl phosphine oxide
COSMO-RS= Conductor-like Screening Model for Real Solvents
CPE = cloud point extraction
DMCEAP = N, N-dimethyl(cyanoethyl)ammonium propionate
DMHEEAP = N, N-dimethyl-N-(2-hydroxyethoxyethyl) ammonium propionate
DNA = deoxyribonucleic acid
FAAS = flame atomic absorption spectrometry
FO-LADS = fiber optic-linear array detection spectrophotometry
FT-IR = fourier transform infrared spectroscopy
HPLC = high performance liquid chromatography
HRE = heat-reflux extraction
HSCCC = high-speed counter-current chromatography
ILAS-MA = ionic liquid aqueous solvent-based microwave-assisted hydrolysis
ILMAE = ionic liquid-based microwave-assisted extraction
ILs = Ionic liquids
IL-SIR-based = solvent (ionic liquid) impregnated resin-based

∗
corresponding author: hangsong@vip.sina.com
146 Yu Cao, Shun Yao, Xiaoming Wang, et al.

ILUAE = ionic liquid-based ultrasonic-assisted extraction

LLE = liquid-liquid phase equilibria
MAE = microwave-assisted extraction
PEG = polyethylene glycol
QSPR = quantitative structure property relationship
RTILs = room temperature ionic liquids
Si-ILs = silica confined ionic liquids
SLM = supported liquid membrane
SPE = solid phase extraction
TODGA = N, N, N’, N’- tetraoctyl diglycolamide
UAE = ultrasonic-assisted extraction
UV-Vis = ultraviolet-visible
VTF = Vogel-Tammann-Fulcher

ABSTRACT
Ionic liquids (ILs) as green solvents are attracting increasing interest from industry
and academic in the whole world during past years. The researches on ILs are developing
at an incredible rate. Their negligible vapor pressure, high thermal stability and relatively
high viscosity make them different from the conventional organic solvents. This review
focuses on the major physical and chemical properties of ILs related to the extraction
application including polarity, pH value, melting point and solubility, etc. The review
take some examples to illustrate the applications of ILs in various subjects of extraction,
including extraction of biological molecular, active components from natural products,
organic compounds from other resources except natural products and metal ions, etc.
Current status of the application of ILs in the extraction and most significant
achievements were reviewed. The comparison between traditional organic solvents and
ILs in the application of extraction suggested that ILs would be a potential excellent
solvent with wide application range in various extraction processes.

Keywords: ionic liquids; property; extraction.

1. INTRODUCTION
1.1. Overview

The ionic liquids (ILs) as a kind of green solvent have been widely used in synthesis and
extraction. As well known, whether a solvent can be a potential extraction solvent is
determined by some specific characteristics, such as density, viscosity, polarity. Certainly, ILs
are not exceptional. The variety of ILs makes it nearly impossible to highlight its property.
Their properties distribute in a wide range except ionic conductivity, but the ILs as extractant
may have some common characteristics. So the properties related to extraction application of
ILs need to be summarized. And ILs have one of most important characteristics is that ILs
can be designed according to their application directions and concrete technical requests, so
the summary in extraction property can also provide useful reference for target synthesis. The
 The Physical and Chemical Properties of Ionic Liquids … 147

ILs mainly used in extraction are imidazole-based. Other two such as pyridinium-based and
N, N-dimethyl-N-R ammonium-based (see Figure1) are also used in extraction technology.
The anion of IL used in extractions involves many types such as BF4-, PF6-, CH3SO4- and
(CF3SO2)2N-.

5 1 5 1
6 6
4
3 3
4
2 2

Non Reducing Anhydroglucose (AGU) or Cellobiose Reducing end group

end group

Figure 1. Three major types of cation of ionic liquids used in extraction.

The length of alkyl chain CnH2n in imidazole-based ILs contains C2, C4, C6 and C8 that
mostly used in extraction process, but the number of carbon atom sometimes may be more
than ten when it is used in the extraction of hydrophobic compounds. At the beginning of this
review, it is introduced about the popular ways of extraction using ILs.

1.2. Extraction Methods

1.2.1. Solvent of Direct Extraction

The ILs as an extractant can be used in many extraction fields and have many benefits in
extraction such as in the treatment of the radioactive wastes. The dispose of the radioactive
wastes was a challenge for chemists and environmental workers. In the past, N, N, N’, N’-
tetraoctyl diglycolamide (TODGA) was considered to have many advantages for extraction of
minor actinides. However, its major drawback is associated with a large volume of n-
dodecane used as a process diluent, which tends to form a third phase with nitric acid [1] and
generates a large amount of the secondary waste. In addition, potential health hazard and
flammability risk are also associated with it [2]. Application of ILs called green solvents
could avoid the above risks due to ILs with low vapor pressure and low toxicity. Besides as
extractant in radioactive wastes dispose, the ILs also were widely reported as extractants in
extraction of metal ions.

1.2.2. Liquid-Liquid Extraction

Liquid-liquid extraction, a conventional extraction method easily used in industrial scale,
was recently used with ionic liquids. There have been lots of reports about aromatic organic
compounds extracted by ionic liquids [3, 4]. With their non-volatile property, the ILs can be
simply recovered to avoid high investment and energy cost which is hard to avoid by using
conventional solvents. The ILs have been widely used in the extraction of benzene, toluene,
ethyl benxene and xylenes, etc. [3]. Shiflett et al. [5] recently extracted the
tetrafluoroethylene and carbon dioxide using 1-butyl-3-methylimidazolium
hexafluorophosphate and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
148 Yu Cao, Shun Yao, Xiaoming Wang, et al.

As a green solvent, ILs may be broad prospects in liquid-liquid extraction process. The
common liquid-liquid extractions with ionic liquids were shown in Table 1 [3, 6-18].

Table 1. The common liquid-liquid extraction systems

Extraction object Extraction phase Ionic liquid Reference

Aromatic Aliphatic [mebupy][BF4]/[Epy][EtSO4] [3, 6-8]
Phenols Aqueous solution [Cnmim][PF6]/[Cnmim][BF4] [9]
Thiophene n-Alkanes [C8mim][BF4] [10]
L-amino acid Ethylacetate/aqueous Amino acid ionic [11,12]
solution liquids/hydrophobic ionic
liquids
Butanol Dilute aqueous [hmim][Tf2N] [13]
solution
Protein Aqueous solution [Btmsim][PF6] [14,15]
Uranium Aqueous solution Hydrophobic ionic liquid [16]
Ferulic Acid/Caffeic Aqueous solution [C6mim][PF6] [17]
acid
Linalool Citrus essential oil [C2mim][Meesu] [18]

1.2.3. Two Phase Extraction

As early as 2003, Rogers and his co-workers reported aqueous two-phase extraction
systems based on ILs and water-structuring salts for the first time [19]. Two-phase extraction
system was different from normal liquid-liquid extraction. In the former extraction the IL
phase directly extracts objects to form a solution. In the latter extraction the IL solution
extracts object and then some IL phase or other reagents used to extract objects in second
time from the IL solution for enriching the objects. The two phase extraction was early used
by the polymer combining with water [20]. But there is another problem that is the polymer
can hard to recover from the water. Hence, the ILs became the objects to form two phase used
in extraction. The ILs can form two phases with many materials such as polymer, water,
phosphate and amino acids [19, 21, 22]. Jiang and co-workers [21] extracted penicillin to
imidazole-terminal PEG-rich phase then used ionic liquid to extract imidazole-terminal PEG,
last they recovered 1-PEG to water for recovering polymer. In the same year, Pei et al.
extracted proteins by ionic liquid-based aqueous two-phase extraction. The ILs can form two
phases with various materials, the IL application in two phase extractions will be extended.

1.2.4. Combined with Other Solid Phase

Solid phase extraction (SPE), which was thought to be as an acceptable alternative to
liquid-liquid extraction, has been widely used in the separation, purification, and solvent
exchange of solutes from a solution [23, 24]. Major SPE mediums related with ILs extraction
technology include anion-exchangeable silica confined IL, ILs on nano-silica sorbents and IL
impregnated resin-based extraction. In those extraction processes with above mediums, ILs
display their functions through different binding ways to various supporters. Silica confined
ILs (Si-ILs) were also already used in chromatographic separation with their excellent
physical and chemical properties [23]. Bi et al. [23] successfully extracted lactic acid from
fermentation broth by anion-exchangeable Si-ILs. Hydrophobic ILs on nano-silica sorbents
 The Physical and Chemical Properties of Ionic Liquids … 149

used in extraction metal from water sample were recently investigated by Mahmoud [25]. In
his research, two newly modified nano-silica sorbents were synthesized. The results showed
that the newly synthesized amino functionalized nano-silica hydrophobic IL sorbents were
experienced with high surface coverage and area as well as high efficiency in lead (II)
extraction providing high metal capacity values compared with other methods [25]. IL
impregnated resin-based (IL-SIR-based) extraction was found to be able to avoid many
drawbacks of conventional SPE method and liquid-liquid extraction [26]. The method of
preparation for the IL-SIR was directly making resin immerse to a solution containing IL. The
IL-SIR-based extraction offers a number of important benefits, such as less consumption of
ILs, retaining properties of ILs, higher mass transfer rate, high recovery rate of target
compounds and easy recovery of the adsorbent [26].

1.2.5. Combining with Membrane

Membrane separation is a conventional separation method and widely used in extraction
technology. The supported liquid membranes (SLM) technique is a combination of three
simultaneously occurring processes: molecule extraction from the feed phase to the SLM,
diffusion through SLM and re-extraction to the received phase [27]. The ILs inject new
vitality to membrane separation technology. The supported membrane includes ILs supported
liquid membrane and hollow fiber supported IL membrane. The technology of ILs supported
liquid membrane coats the liquid membrane with IL and needs low investment and operating
cost, low energy consumption, low liquid membrane requirement and simple to operate [28].
The SLM was thought to have wide application areas involving extraction of organics from
water, gas, amino acids, toxic metal ions from their aqueous solution and separation of
isomeric organic compounds [29]. The unique properties of ILs were thought to have
potential application in industrial separation for membrane technology. Malik et al. [29]
reviewed the IL supported liquid membrane techniques and Lozano et al. [27] summarized
the recent advances in supported IL membrane technology. Hollow fiber based liquid phase
microextraction was introduced in last century and it has been widely used in separation
process. In this process, one most important factor is the selection of organic solvent which
determines the extraction efficiency. Toluene and 1-octanol are usually selected as
conventional solvents. ILs have been proven as a good solvent in this process [30] and display
excellent extractability for various organic compounds and metal ions. Hollow fiber
supported IL membrane microextraction was used in determination of sulfonamide and
chlorophenols and so on. Furthermore, ILs can make the subsequent analysis simpler.

1.2.6. Ionic Liquid Supported Cloud Point Extraction

Cloud point extraction (CPE) is a novel separation and pre-concentration technology.
When the nonionic surfactant solution is at a concentration at least 3~20 times of its critical
micelle concentration (CMC) and at a temperature higher than its cloud point, phase
separation occurs [31]. Conventional surfactant such as polyethoxylated nonionic surfactants
and non-ionic surfactant Triton X-114 were usually used as the separation agent in CPE
procedure [2, 3, 32] and this technology has been used in various samples and objects [2, 3,
32, 33]. Recently ILs were found to be used in cloud-point extraction [34] because that ILs
were gaining recognition as unique solvents for environmental applications and its usage in
CPE technology has far-reaching significance. BMIM PF6 has been examined for CPE by
Pavagadhi et al. [34] in their paper. In their study, the IL was used to treat the water by
150 Yu Cao, Shun Yao, Xiaoming Wang, et al.

removing the most commonly reported toxin microcystin-leucine-arginine (MCLR). For

environment and health requirements, the environmentally friendly pre-concentration
methods are needed without compromising the sensitivity and specificity of the conventional
methods. Therefore, ILs as a green solvent was a good choice to meet those requirements and
the results showed excellent application in CPE.

1.2.7. IL Dispersive Liquid-Liquid Microextraction

The microextraction was mainly used in trace determination of samples before detection
by various chromatography methods. Microextraction techniques are very useful and popular
for the pre-concentration and separation of organic and inorganic contaminants in
environmental samples at trace levels since the last ten years. In addition, the liquid-liquid
microextraction was also used in treatment of natural products. It has many advantages like
simple procedure, high extraction efficiency and low consumption of toxic organic solvents
[35]. The ILs dispersive liquid-liquid microextraction has been used in extraction and
enrichment of target analytes for various analytical methods such as high performance liquid
chromatography (HPLC), capillary electrophoresis (CE), flame atomic absorption
spectrometry(FAAS) and fiber optic-linear array detection spectrophotometry (FO-LADS).
With the appearance of more and more new ILs, the IL dispersive liquid-liquid
microextraction will be used in wider areas.

2. RELATED PHYSICAL AND CHEMICAL PROPERTIES

As everyone knows, the practicability of the application of ILs, especially in extraction
was considerably determined by physical and chemical properties of ionic liquids such as
density, viscosity, polarity, pH value and so on. However, the designability of properties is
one of most important characteristics and advantages of ILs. Previous researches also showed
that the design of properties-suitable ILs for specific requirement was totally feasible. For
example, according to the regular relationship between the polarity and structure of ILs, the
ILs with certain polarity can be designed. Obviously, a clear understanding about ILs’
physical and chemical properties is crucial for its application in extraction.

2.1. Density

The density of ILs will determine the separation form of ILs in extraction process. The
density is the most often measured and reported physical property of ILs for its importance in
related applications. ILs are generally denser than organic solvents, with typical density
values ranging from 0.9 to 1.7 g cm-3. Many of the reported density values are at a single
temperature, usually at 20 or 25 oC. The density of ILs versus pressure and temperature has
also been modeled. Considerable amounts of data on the density of ILs are available in the
literatures and reports of temperature parameters (always linear) are most valuable.
In general, the density of matter is not only related with the temperature and pressure, but
also with the relative molecular mass, the interaction between molecules and molecular
structure. The density of ILs is greatly affected by the anions and cations. Anion is usually
 The Physical and Chemical Properties of Ionic Liquids … 151

more significant on the density. Via comparing the imidazole cations with different
substituents, the density is linear to the alkyl chain length of substituents. Larger organic
cations usually have lower density. The density was affected by the molecular weight of the
anions, which was related to the molecular frame volume and free volume of the room
temperature ionic liquids (RTILs). In particular, the density significantly varies according to
the conjunction (single bond, double bond, chainlike, or cyclic) and conformation (planar or
non-planar) of the species.
Reported densities of ILs vary between 0.9 and 1.7 g cm−3 and are little sensitive to
temperature [36]. For example, Kato and Gmehling [37] presented data for 1-butyl-1-
methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide in the range of (298.15~323.15)K, it
showed variation of only 0.9% in the density.
Fisher Company [38] provided a density formula for dialkylimidazolium IL at different
temperatures:

ρ = a + b (T- 60)

where ρ is the density in kg·m-3; T is the temperature in K; a, b were estimated by published

experimental data.

Table 2. The coefficients a and b of some ionic liquids

Ionic liquid a/(g/cm3) b/10-4(g/cm3K) Ionic liquid a/(g/cm3) b/10-4(g/cm3K)

[BMIM]BF4 1.1811 7.6229 [OMIM]PF6 1.1960 9.2302
[HMIM]BF4 1.1242 7.2090 [HMIM]Cl 1.0593 6.3026
[BMIM]PF6 1.3381 8.5275 [OMIM]Cl 0.9999 3.6033
[HMIM]PF6 1.2596 10.2938

Fredlakc [39] gave a deep research on the density of ILs at different temperatures. When
the temperature rises, the volume of all the ILs has different degrees of expansion, which
leads to the decrease of the density.
Since it is difficult to study properties of all compounds at different conditions, it is
necessary to find a method to estimate properties of compounds. It seems very important to
predict the property before an IL is synthesized for its functionality. The quantitative structure
property relationship (QSPR) is often used to predict density of ILs. The record indicates that
QSPR models could give a reasonable prediction of unknown or unavailable compounds of
the same class. Trohalaki et al [40] reported a QSPR method to estimate the density.
There have been some other methods in the estimation of the IL density. Gardas et al.
[41] successfully extended Ye and Shreeve’s group contribution method [42] for a wide range
of temperature and pressure.
In this method, the average relative deviation of estimated densities for imidazolium-
based and phosphonium-based ILs can be 0.45% and 1.49%, respectively. And some other
methods were reported to estimate the temperature-dependent densities of ILs. In Ref [43], a
different estimation method of the heat capacity and temperature-dependent density of ILs
was presented.
152 Yu Cao, Shun Yao, Xiaoming Wang, et al.

2.2. Viscosity

Viscosity is another important factor of ILs in affecting its application in extraction,

which is generated by the motion and molecular interaction between the molecular. Viscosity
of ILs usually is reported as the dynamic viscosity and also called the viscosity coefficient.
Most ILs are viscous liquids and inherently much more viscous than molecular solvents.
Viscosities of ILs vary over a range of <10 to >1000 cP at room temperature. Viscosity
affects diffusion of solutes and practical issues, such as stirring and pumping. So, high
viscosity is a major disadvantage since it negatively will affect mass transfer and power
requirements for mixing in heterogeneous liquid-liquid systems.
Viscosity-temperature dependence of ILs is more complicated than that of most
molecular solvents, because most ILs do not follow ordinary Arrhenius behavior. Most
temperature studies fit the viscosity values to the Vogel-Tammann-Fulcher (VTF) equation,
which adds an additional adjustable parameter (glass transition temperature) to the
exponentially term.
The increase of length of alkyl chains of the cation does not necessarily result in a
monotonous increase in the viscosity. Huddleston et al. [44] found that for the series of
[CnMIM][PF6] with n in alky chain of [CnMIM] equal to 4, 6 and 8, the viscosity at 25 oC
increased monotonously from (450 to 682) mPas. Bonhote et al. [45] found that for alkyl
chain lengths from 1 to 4 on 1-alkyl-3-methylimidazolium Tf2N−, the viscosity first
decreased and then increased again. At present it is believed that there is insufficient data on
fluids of well defined purity to make any definitive conclusions. As noted, the high viscosity
of ILs does not appear when ILs are used in chemical processing. These high viscosities
facilitate suspending larger drops at the tip of a capillary or needle for liquid-phase
microextraction but otherwise contribute to poor penetration of porous solid materials and
restrict mass transfer at solvent interfaces [46]. MacFarlane et al. [47] prepared a new family
of RTILs based on the dicyanamide anion N(CN)2−. Among them, [Emim][N(CN)2] has a
melting point at −21◦C and its viscosity at 25◦C is 21mPa s. Liquids with viscosities of this
magnitude would not present processing problems. This is a limitation for some methods such
as countercurrent chromatography. The viscosity of ILs can be lowered into a useful range for
some applications by increasing the temperature or by dilution with a miscible solvent [48].

2.3. Melting Point

The melting points of IL solvents define the lower end of the liquidus range. Compared
with molecular solvents, the low vapor pressure and very wide liquids range are probably the
two meaningful properties that make the ILs very attractive as solvents. Many or most ILs are
prone to supercooling, which makes melting points difficult to measure. Many ILs can form
glasses and ILs’s glass transition temperatures are usually reported instead of melting points.
The glass transitions tend to be very low (<−50 ◦C) and viscosity very high at such cold
temperatures, so the solvents are not really useful for most reaction chemistry at sub-zero
temperatures (except for situations where glassy media are desirable).
For a substance to be considered as a RTIL, its melting point should be below 100 ◦C.
The main factors that influence the melting point are the charge distribution on the ions, H-
bonding ability, the symmetry of the ions and the van der Waals interactions. The melting
 The Physical and Chemical Properties of Ionic Liquids … 153

points of many ILs are very uncertain because they undergo considerable supercooling. The
supercooling of ILs causes their freezing point to be notoriously unreliable and
irreproducible.
References [49-52] made systematic studies of the influence of the alkyl chain on the
melting points of RTILs. In general, the melting point, if observed, decreases from the methyl
substitution to the butyl to hexyl compound and then increases. However the studies come to
different conclusions because in some studies only glass temperature transition was observed
for many of the C4 to C8 compounds. Some of the glass transition temperatures were reported
as melting points.
Katritzky et al. [53] used QSPR to predict the melting points for 126 structural diverse
pyridinium bromides. They found that the statistically most important parameters were the
coordination ability of cations determined by molecular shape and symmetry, electrostatic
intermolecular interactions and the number of conformational and rotational degrees of
freedom in the solid and liquid phases.

2.4. Polarity

Solvents polarity is another important factor which remarkably influences ILs application
in extraction, more knowledge about the polarity of ILs can give a positive impetus to the
further application of ILs.
Due to the multitudinous peculiar features of ILs compared with the ordinary molecular
solvents, we can not lump together the polarities of ILs and molecular solvents. The solvent
polarity can not be simply defined, but we often consider polarity as an indicator of the
combined strength of specific solute–solvent interactions and nonspecific solute-solvent
interactions. The special solute-solvent interactions, according to the previous study on the
polarity in ILs, can be understood as the same mechanism of that in ordinary molecular
solvents to a certain extent. The nonspecific solute-solvent interactions, such as electrostatic
interaction, appeared to be more complex and unpredictable.
To investigate the polarity of ionic liquids, the methods researchers commonly use
include solvatochromic dyes and partition coefficient methods and so on [54]. Among them,
the most common method is using solvatochromic dyes, which are a variety of compounds,
such as Nile Red and betaine-30, for which the absorption or emission band maxima varies
with the polarity of the solvents in which they are dissolved. Through the comparison
between the absorption spectra of solvatochromic dye in series of conventional solvents and
ionic liquids, the polarity of the ILs can be determined.
On the study of the polarity of ILs a lot of significant work has been done. For example,
Carmichael and Seddon [55] used Nile Red to investigate the polarity of room-temperature
ILs based on the 1-alkyl-3-methylimidazolium cation. Their research provided information
about their relative polarity and trends within the series, and the polarities in these ILs
appeared in the same region with 2-aminoethanol and the lower alcohols, such as methanol,
ethanol and 1-butanol, etc.
Kobrak’s work [56] showed that there is definite relationship between the polarity and
the molar volume in ionic liquids. Although the results were not quantitatively accurate, the
study made the prediction of polarity of ionic liquids possible, and furthermore, researches
can design polarity-specific ionic liquids according their research requirements.
154 Yu Cao, Shun Yao, Xiaoming Wang, et al.

Znamenskiy and co-workers’ research [57] showed that controlling the polarity of ILs
through the specific interactions is feasible. They neglected the nonspecific interactions and
only considered the specific solute-solvent interactions, and then the variety of the polarity of
ILs can be seen as a function of ionic structure.
Anyway, because of the hydrophobic of alkyl chains, as same as ordinary organic
compounds, ILs with long chain branching are generally hydrophobic, while those
hydrophilic ILs always has no chain branching or their chain branching are very short.
Correspondingly, the longer the chain branching of ILs is, the stronger polarity ILs have.

2.5. Acid and Basicity of Ionic Liquids

2.5.1. Acid Ionic Liquid

Acid ILs can be divided into Lewis acid and Brønsted acid ILs. The lewis acids were
obtained by mixing the metal halide and Halogenated phosphorus salt by different mole
fraction, for example, the ILs [BMIM]Cl/ZnCl2, [BMIM]Cl/CuCl, [BMIM]Cl/FeCl3 and
[BMIM]Cl/AlCl3.
Brønsted acid ILs were obtained by introducing acid groups. Common Brønsted acids are
shown in Figure 2. The acidity of Brønsted acids is determined by their acid group.
According to reference [38], when chain length of carboxylic acid chain increased, the acidity
of imidazole based ILs decreased such as [C5emim]+<[C4emim]+<[C3emim]+. When the
cations of ILs were the same, the acidity of ILs changed by the following order: Cl->BF4-
>CF3SO3-.
The acidity of anions in ILs may influence the extraction efficiency. Imidazole based ILs
with different anions were studied to show the influences of acidity of anion in extraction.
The acidity order of anions was as follows: PF6>Tf2N> BF4.
The methods to detect the acid ILs were reported by some researchers. Wang et al. [58]
overviewed these methods mainly containing Hammett indicator method, Potentiometric
titration method and FT-IR probe molecular determination method. The Hammett indicator
method has been widely used to approximate the acidity of a pure IL. Cox et al. [59] used 3-
nitroaniline as an indicator to measure the Hammett acidity. The IR spectrum by using probe
molecular with special absorption peaks can be used to detect the acidity of different solid
and liquid Lewis and Brønsted acidic substances. Pyridine is the most commonly used probe
molecular and will change the position of IR absorption peaks of ILs when it is added into the
latter. Cao et al. [60] used FT-IR method by employing acetonitrile as molecular probe to
characterize the [bupy] BF4-MCl3 (M = Al, Fe) ILs. They found the acidity strength of [bupy]
BF4-AlCl3 was stronger than [bupy] BF4-FeCl3. Potentionmetric titration method is mainly
used to study the ion exchangers for ILs [61]. Zhao et al. used this method detected the
acidity of a series of ILs [38].

SO3H
R N N (CH2)nCOOH N N
N N
- - -
CF 3SO 3 X HSO 4

Figure 2. Several common Brønsted acidic ionic liquids.

 The Physical and Chemical Properties of Ionic Liquids … 155

2.5.2. Basic Ionic Liquid

Similar to acid ILs, basic ILs also can be divided into Lewis basic and Brønsted basic
ILs. Mehnert found the neutral ILs such as [BMIM] BF4 can become basic ILs mixed with
strong base such as NaOH or KOH [38]. Li et al. [62] summarized the basic ILs in his review.
Besides the ILs from the strong base, some new basic ILs were reported by researchers [63,
64]. The Brønsted basic ILs was prepared by introducing basic groups. Common basic ILs are
showed as Figure 3. The basity of Brønsted acids were decided by their basic group, and their
basity levels were decided by the basity levels of the basic groups.

NH2 ONa
N N N N N N N
CH2CH2OH
OH- BF4- OH- X-

Figure 3. Several basic ionic liquids.

The reports about basicity detection of ILs were rare. Some researchers [65] used
Hammett indicator method to identify the basicity of ILs. But these methods only gave a
qualitative result by comparing with traditional base such as NaOH [wenxian]. The basity
order of ILs was as follows: [Bmim][OH] > [Bmim][IM] and [NH2Emim][IM]>
[NH2Emim]Br. The characterization of basic ILs need advance investigation.

2.5.3. The Acid and Basic Ionic Liquids in Extraction

The acidity-activity relationship has been studied by many researchers. There were
seldom studies about the relationship between acidity or basicity and extraction efficient. But
the influence of pH value in extraction procedure was found to be a very important factor in
actual applications, which could influence the partition coefficients of the extraction object
and determine the presence species of object. When the ILs are used in extracting acids, the
extraction rate would increase if the basity of anions is stronger. For example, in the
extraction of 3-indole butyric acid, the percent extraction was higher by using CnmimBF4 than
that using CnmimPF6 [66]. When the ILs were used in extraction, the pH value of extraction
systems was almost lower than pka value of the used ILs to maintain the combination ability
of with the anion of ILs.

2.6. Solubility

When in choice of ILs for extraction application, the solvation ability is always a key
factor, because the solvation ability of ILs actually directly determines if it can be employed
as an extraction solvent. Consequently knowledge about the solvation characteristics of ILs is
essential to the use of ILs in separation.
For the ordinary dipolar liquids such as acetonitrile, forming a space to offer to solute
molecule needs a cost of some units of kcal/mol to remove some solvent molecules, while in
ILs it needs a cost of some hundreds of kcal/mol. This is because every ion in ILs is
surrounded by a discrete number of counter ions. Only when the solute-solvent interaction
can overcome the needed energy, the solvation can occur.
According to Amstrong and co-workers’ research, ILs can dissolve solutes through a
variety of forces, such as dipole-dipole interaction, hydrogen bond, π-π interaction of
156 Yu Cao, Shun Yao, Xiaoming Wang, et al.

imidazole ring and so on [67]. Rogers and co-workers’ showed that neutral substances have
better solubility in ILs, while the ionized substances tend to be dissolved in water rather than
in ILs [68].
However, the solvation mechanism in ILs is not clear yet; some studies think mechanism
of ILs is similar to that of polar organic solvents. Because of many unique properties of ILs,
we can not consider the dissolving behavior in ILs as same as that in ordinary organic
solvents.
Despite the lack of adequate understanding of the solvation mechanism, considerable
achievements on the study about the solvation in ILs have been made. For example, previous
research showed that ILs could dissolve a wide and varied range of organic and inorganic
compounds in reasonable mole ratios. Most of ILs could form homogeneous system with
polar organic solvents such as ethanol and acetone, while biphasic system could form if ILs
are mixed with water or low polar organic solvents, such as acetic ether, ether and
methylbenzene, etc. [69].
In recent years, the study on the separation in two-phase systems with a pure IL phase has
been getting more and more attention. For example, it has been proved that [Bmim][BF4] can
be used to extract erythromycine-A by Cull et al [70]. There is also a few researches to find
that when [C6mim] [PF6] was used to extract the amino acids the partition coefficients were
pretty high [71].
After all, because most ILs have strong polarity, they can dissolve many organic or
inorganic compounds and polymeric materials. And they can also dissolve hydride, carbide,
nitride, oxides and sulfides [72]. Obviously, satisfactory solvation ability makes ILs very
attractive as extraction medium.

2.7. Binary Property

A clear understanding of liquid-liquid phase equilibria (LLE) between ILs and organic
solvents is of great importance to the related application of the ILs, especially in the industrial
application point of view, because it determines whether the ILs can be easily reused to a
certain degree. Simultaneously, LLE also plays a key role in the extraction process.
According to previous researches, in a binary system comprised of IL and alcohol, factors
including the alcohol chain length, the cation chain length and subsistent groups of ILs all
influence the phase behavior [73]. For instance, the solubility of ILs in alcohol normally
usually decreases with the growth of the number of the C atoms the alcohol has, and the
miscibility between ILs and water shows apparently decreasing with the increasing of cation
chain length.
The study of Andreia Forte et al [74] proved that both the structure of ILs and alcohols
affect the phase behavior. They investigated twenty binary systems containing ILs, and the
results showed that the systems comprised of hydrophilic dicyanamide ILs and
polyhydroxy alcohols were completely miscible, while the systems containing
Bis(trifluoromethylsulfonyl)amide ILs show low solubility with butane-1,2-diol and its
structural isomers.
Considering the huge number of ILs, however, it’s impossible to actually measure all the
systems. In view of this, Klamt et al [75] proposed a model called Conductor-like Screening
Model for Real Solvents to predict the LLE of binary systems. This model can almost be
 The Physical and Chemical Properties of Ionic Liquids … 157

suitable for all possible ILs and hydrocarbons mixtures. Although it is unable to provide the
accurate data of LLE, the systems can be designed to satisfy our need according the
qualitative trend of the phase behavior it predict.
About the prediction of the properties of binary systems, Navia and co-workers [76] also
did some meaningful works. Their research showed that there were not too much excess
properties in binary systems comprised of ILs and other solvents, which meant the properties
of binary mixtures could be accurately predicted based on the pure compound properties.

3. EXTRACTION APPLICATIONS
3.1. Extraction of Metal Ions

More and more metallic substances in the environment caused by human’s

industrialization have been a serious threat to ecological environment and, in extreme case,
human healthy. For lots of heavy metals ions, such as cadmium, once they enter the human
body, it is hard to be excreted from the body and the concentration will be increasing through
the accumulation, and it reaches a certain concentration which even leads to the death.
Besides the harmfulness of the metals to environment, sometime the recovery of valuable
metals, such as silver, is also worthy to do from an economic point of view.
Obviously, a simple and effective separation of metals is of significant importance. In
past, methods like precipitation, solvent extraction and ion exchange method were taken to
remove or recover metals [77], and among them solvent extraction shows many advantages
and has been widely used. However, the conventional solvent extraction makes secondary
pollution caused by the volatility of the organic solvents. As mentioned above, the use of ILs
can treat this situation for their nonvolatile. ILs as an extractant has been fairly widespread.
But the extraction mechanism is still controversial yet, and the most convincing point is
cation-exchange mechanism [78], that is metal cation transferring to the ILs phase through the
metal cation exchanging with the cation of IL.
About the extraction mechanism lots of work have been carried out. For instance,
Kazunori Nakashima and co-workers used octyl (phenyl)-N, N–diisobutyl carbamoyl methyl
phosphine oxide (CMPO) to extract rare earth metals from aqueous solutions, and the results
showed that the extraction efficiency and selectivity was higher than that when using the n-
dodecane as extractant. Moreover, they also found that the extraction efficiency of the IL
system decreased with the increasing of [Bmim]+ concentration, while the dodecane system
showed no relationship with the [Bmim]+ concentration at all. This phenomenon confirmed
the cation-exchange mechanism to a certain extent.
De los Rios and co-workers [79] investigated the extraction of Zn2+, Cd2+, and Fe3+ from
aqueous hydrochloride solutions using six ILs [MTOA+][Cl-], [omim+][BF4-], [omim+][PF6-],
[bmim+][PF6-], [bmim+][NTf2-] and [omim+][NTf2-], as exhibited in Figure 4. The results
showed that [MTOA+][Cl-] can almost completely extract the all three metal ions, and so do
the [omim+][BF4-] for the Zn2+ and Cd2+. Furthermore, because there is no extraction of Fe3+
using [omim+][BF4-], [omim+][BF4-] can selectively extract Zn2+ or Cd2+ from Fe3+ .
Similarly, [bmim+][PF6-], [bmim+][NTf2-] and [omim+][NTf2-] can also make selective
158 Yu Cao, Shun Yao, Xiaoming Wang, et al.

separation of Cd2+ or Fe3+ from Zn2+ possible. All of these results demonstrated that the
application of ILs in extraction of metals is very promising.

R=(CH2)3CH3 1-butyl-3-methyl-3H-imidazol-1-ium (bmim+)

N N
R R
R=(CH2)7CH3 1-butyl-3-methyl-3H-imidazol-1-ium (omim+)

R1=(CH2)7CH3 Methyltrioctylammonium chloride (MTOA)

R1 N R1

R1 O O
F3C N CF3
S S
Cl-
O O
-
Chloride (Cl ) Bis(trifluoromethylsulfonyl)imide (NTf2-)

F
F
F F
F B F
P
F F
F
F
Hexaflurophosphate (PF6-) Tetrafluoroborate (BF4-)

Figure 4. Ions involved in the assayed ionic liquids [76].

Papaiconomou and co-workers [80] also achieved the selective extraction of copper,
mercury, silver and palladium ions from water using hydrophobic ILs as extractant. They
compared ten ILs and the results in their study showed that all the studied ILs formed two
liquid phases when mixed with water, and except that mercury ion could be extracted well by
the ILs containing octylpyridinium cations, other metal ions were not significantly extracted
by all these ILs.
Moreover, it was reported that the following ions Cd2+, Hg2+, Co2+, Ni2+ and Fe3+ can be
extracted with [BMIM][BF4] and [C6MIM][PF6] [81]. Cs+ and Sr2+ can be extracted using ILs
in the presence of crown ether [82]. And selective extraction of Cu2+ and Ag+ using ILs were
proved to be feasible by Wei, etc [83]. Luo and co-workers showed K+ and Na+ can also be
extracted by ILs [84].

3.2. IL Extraction of Organic Molecules

The specific advantages and limitations of ILs in these studies were discussed with a
view to defining the future uses of IL extraction. ILs are good solvents for a wide range of
compounds in which they behave as polar solvents. Their physical properties of note that
distinguish them from conventional organic solvents are a negligible vapor pressure, high
thermal stability, and relatively high viscosity. In this section, the extraction of phenolic
compounds will be as an example to show the application of ILs in separation on organic
 The Physical and Chemical Properties of Ionic Liquids … 159

compounds. As illustrated in Table 3 [85-89], phase partitions of many phenolic compounds

are summarized in the IL-water biphasic systems.

Table 3. Examples of IL extractions of organic/bio/biofuel molecules

Substances IL Extractant Reference

Phenolic Phthalic acid, aniline, 4- [BMIM][PF6] none [85]
compounds hydroxybenzoic acid,
benzoic acid, p-toluic acid,
benzene, chlorobenzene,
Phenol, tyrosol, p-
hydroxybenzoic acid
Amino acids Chlorophenols, Tryptophan, [BMIM][PF6] DC18C6 [86]
glycine, alanine, leucine,
lysine, arginine
Carbohydrates Xylose, fructose, glucose, [CnMIM][X] (n none [87]
sucrose = 4, 6, 8, 10;
X = Cl−, PF6
−
, BF4
−
)
Organic acids Lactic acid, acetic acid, [CnMIM][PF6] TBP (in [88]
glycolic acid, propionic (n = 4, 6, 8) some
acid, pyruvic acid, utyric cases)
acid

Another process was developed to separate C4-8 diolefin hydrocarbons (such as

butadiene) from at least one diolefin and at least one C1-18 paraffin using ILs (such as
[BMIM][BF4] [89]). A continuous extraction process using IL to separate C6-9-aromatic
hydrocarbons has also been developed, from benzene-rich petroleum streams [90].
The academicians are often overtly optimistic while laboratory analysts have a long
tradition of conservativism. What is clear is that the proof of concept and feasibility studies
completed in academia has not obtained sufficient weight so far to establish the use of room
temperature ILs in routine laboratory practice. The green shoots of development seem closer
to fruition in process chemistry driven mainly by the unique physical properties of ILs that
allow them to be used as economic and environmentally friendly eplacements for
conventional organic solvents at a time when such actions are seen as being politically
correct.
More recently, various ILs were found to be green solvents for cellulose dissolution [91]
and suitable reaction media for cellulose functionalization [92]. The high concentration of
chloride and its activity in ILs are considered to play an important role in cellulose
dissolution, which is highly effective in breaking the extensive hydrogen- bonding network
present in cellulose. A similar observation on the degradation of cellulose in ILs was reported
by Heinze et al.[93]. They found that the dissolution of spruce sulfite pulp and cotton linters
in [C4mim]Cl led to slight degradation, and DP of cellulose after regeneration decreased from
593 to 544 for spruce sulfite pulp and from 1198 to 812 for cotton linters, respectively.
160 Yu Cao, Shun Yao, Xiaoming Wang, et al.

3.3. Extraction of Bioactive Components from Natural Products

Currently, ILs have been successfully used in extraction of bioactive components from
natural products (as shown in Table 4) [34, 94-109] in these years. The advantages of using
microwave-assisted extraction (MAE) in the extraction of organic compounds directly from
solid matrix have been demonstrated in recent years, and it is considered that ILs can
efficiently absorb microwave energy as solvents and co-solvents [110]. Application of ILs as
solvent in MAE of bioactive components from natural products was reported by many
research groups. A series of 1-alkyl-3-methylimidazolium ILs with different alkyl chain and
anion composition were evaluated with their extraction efficiency. The obtained results
indicated that the anions and cations of ILs had influences on the extraction efficiency. Du
and coworkers [97, 98] were developed IL-based microwave-assisted extraction (ILMAE)
methods for extraction trans-resveratrol from Rhizma Polygoni Cuspidati and lycorine,
lycoramine and galanthamine from Lycoris, and the results demonstrated the potentiality of
ILs as alternative solvents in MAE. Compared with HRE technique, ILMAE could obtain
higher extraction yield by using less solvents at short extraction time. And in their latest
article, the application of acid ILs aqueous solvent-based microwave-assisted hydrolysis
(ILAS-MAH) technique was developed for the extraction of myricetin and quercetin from
Myrica rubra (M. rubra) leaves [95]. Different from the conventional procedures, the
proposed ILAS-MAH was a rapid and effective method with a higher yield without volatile
solvent consumption. Chi and co-workers [104] investigated a microwave-assisted extraction
method to extract senkyunolide I, senkyunolide H and Z-ligustilide from Ligusticum
chuanxiong Hort, and two protic ILs, N, N-dimethyl-N-(2-hydroxyethoxyethyl) ammonium
propionate (DMHEEAP) and N, N-dimethyl (cyanoethyl) ammonium propionate (DMCEAP),
were employed as extractants. After extraction, IL was extracted by n-hexane to recover
target compounds. The concentration of senkyunolide I and senkyunolide H hardly decreased,
but the concentration of Z-ligustilide decreased by 39.7%, these results might be caused by
the solubility of the protic ILs towards the organic solvent. The extraction mechanism of the
investigated microwave assisted ILs extraction was the same as traditional organic solvent
extraction.
IL surfactants are a class of ILs, which can form micelles in the aqueous solution. Wu
and coworkers [96] developed a novel extracting system based on the use of IL surfactants in
ultrasonic-assisted extraction (UAE) of tanshinones from Salvia miltiorrhiza bunge, and they
found that the carbon chain length exerts a significant impact on the extraction performance,
and no traditional organic solvents was used in the extraction, which made this method
environmentally friendly and more attractive than the conventional organic solvent-based
extraction. UAE as one of the promising extraction techniques can offer high reproducibility
in shorter time, simplified manipulation, reduced solvent consumption and temperature and
energy input [111]. Cao group investigated an IL-based ultrasonic-assisted extraction
(ILUAE) method for extraction piperine from white pepper powder [102]. Compared with the
conventional heat-reflux extraction (HRE) and regular UAE, the optimized approach gained
the highest extraction efficiency (from 1.950% to 3.577%) within the shortest extraction time
(from 2 h to 30 min). Sun and coworkers developed an IL based ultrasonic-assisted extraction
method for the extraction of the three isoflavones, tectoridin, iristectorin B and iristectorin A
from Iris tectorum Maxim, which were separated and purified by high-speed counter-current
chromatography (HSCCC) [98]. Under the optimized ILUAE conditions, the highest
 The Physical and Chemical Properties of Ionic Liquids … 161

extraction yields of tectoridin, iristectorin B and iristectorin A were 37.45, 2.88 and 5.28
mg/g, respectively. These results indicated that the combination of application of ILUAE and
HSCCC was a very powerful technique for the extraction and preparative separation of
tectoridin, iristectorin B and iristectorin A from I. tectorum dried roots.

Table 4. Extraction of effective components of natural products

Extraction
Source Ionic liquid Target compounds
method
Myrica rubra leaves[95] [BMIM][HSO4] Myricetin and quercetin MAE
tanshinoneI, tanshinone
Salvia miltiorrhiza
[C16MIM][Br] (IL surfactant) IIA, and UAE
bunge[96]
cryptotanshinone
lycorine, lycoramine and
Lycoris radiata[97] [BMIM][Cl] MAE
galanthamine
Rhizma Polygoni
[BMIM][Br] trans-resveratrol MAE
Cuspidati[98]
Tectoridin, iristectorin B
Iris tectorum Maxim[34] [OMIM][Br] UAE
and iristectorin A
Lonicera japonica
[BMIM][BF4] Chlorogenic acid UAE
Thunb[99]
the fruit of Schisandra Biphenyl cyclooctene
[C12MIM][Br] UAE
chinensis Baill [100] lignans
Nelumbo nucifera Gaertn [BMIM][BF4] and Liensinine, isoliensinine
MAE
.[101] [HMIM][BF4] and neferine
White pepper (Piper
[BMIM][BF4] Piperine UAE
nigrum L.[102]
Cynanchum
[BMIM][Cl] Paeonol LLE
paniculatum[103]
N,N-dimethyl-N-(2-
hydroxyethoxyethyl)
Ligusticum chuanxiong ammonium propionate
lactones MAE
Hort.[104] (DMHEEAP) and N,N-
dimethyl(cyanoethyl)ammoni
um propionate (DMCEAP)
Saururus chinensis
(Lour.) Bail. (S.
[BMIM][Tso] Rutin MAE
chinensis) and Flos
Sophorae[105]
Stephaniae Fangchinoline and
[BMIM][BF4] UAE
tetrandrae[106] tetrandrine
N-nornuciferine,O-
lotus leaf[107] [HMIM][Br] nornuciferine, and MAE
nuciferin
Psidium Guajava Linn. Gallic acid, Ellagic acid,
leaves and Smilax china [BMIM][Br] Quercetin, tran- MAE
tubers[108] Resveratrol
Corydalis saxicola
[HMIM][Br] Dehydrocavidine MAE
Bunting[109]
162 Yu Cao, Shun Yao, Xiaoming Wang, et al.

3.4. Extraction of Biological Substances

Biological substances were different from other materials due to their unique application
and potential prospects in the areas about food, health, environment and energy. The
extraction of biological substances here refer in particular to the application of ILs in the
extraction of the substance about protein, amino acids, enzyme, biofuel and biofeedstock,
which has many restrictions due to their unique properties and their special uses. The
traditional toxic organic solvent sometimes can not be used in the extraction of some
substances when the productions are used in the areas of food or health. Furthermore, the
extractants in extractions of biological substances have many limitations in their some
physical properties. Taking the protein for example, the protein is sensitive to pH value,
temperature, metal salt and some organic solvents which all may cause protein inactivation or
degeneration. ILs have been successfully used in the extraction of protein for a few years.
This section will take some examples to illustrate the application of ILs in the relative
extraction process.

3.4.1. Proteins
The first example that showed is that the extraction of proteins by using ILs. The proteins
about life technology are not suited to toxic organic solvent. The green ionic liquids became
the alternative extractant to be employed in processing proteins. The extraction of proteins by
ILs has several characteristics as follows:
First, early extraction of proteins by using ILs needed a concomitant extractant or two-
phase extraction for the low solubility of proteins in ILs. Proteins of bovine serum albumin,
trypsin, cytochrome c and γ-globulins were extracted efficiently by aqueous two-phase
extraction systems based on imidazolium ILs [112]. With the development of extraction
research, Cheng et al. [113] reported that the heme-protein was extracted into IL without
using any concomitant reagent or extractant in 2008 for the first time. In their study, the
hemoglobin was been extracted from human whole blood with BtmsimPF6 and the
quantitative extraction had arrived a certain level. The directly extraction by using ILs will
extend to more proteins with the target synthesis of novel ILs.
Second, the extraction environment was various and this suggested that ILs can be used
in many complex conditions. The extraction objects include yeast, blood and so on [113,
114]. Yeast is thought to be an important model in the study of biological science. It is not
only used in the research of genetics and basic biological process of cells, but also the
industrial production of various proteins. But the harder cell wall make it is more difficult to
get proteins from it. Recently, ILs were used in cell disruption stage for extraction of proteins.
The investigation of Ge et al. [114] indicated that the IL [DMAPA]FA was a promising
reagent for protein extraction in yeast cells.
Third, the IL can be used in the extraction of different kinds of proteins such as
hemoglobin, bovine serum albumin, trypsin, cytochrome c, and γ-globulins.
Finally, the extraction of proteins by ILs was influenced by many factors and the activity
of proteins could be maintained after extraction. The protein extraction was influenced by
temperature, pH value and IL concentration. One most important thing in protein extraction
was that the conformation and activity of proteins can not be changed in the whole extraction
procedure. The research of Pei et al. [112] suggested that both the conformation and activity
 The Physical and Chemical Properties of Ionic Liquids … 163

were maintained in the IL-rich phase of the aqueous two-phase system, hence it proved the
safety of ILs indirectly. Besides directly extracting proteins, the ILs have also been indirectly
used in these procedures.

3.4.2. Animo Acids

Amino acid is an important biological molecular and the basic unit of proteins. The
amino acids have been widely used in food and health. As an important nutrients and drugs,
the recovery process of amino acids is necessary. Some amino acids (L-tryptophan, L-
phenylalanine, L-tyrosine, L-leucine and D-valine) were recovered from aqueous media by
ILs [115]. The ILs were used in extracting neutral, acid and basic amino acids. Absalan et al.
employed imidazolium-based ILs as extractant to study the partitioning behaviors of typical
neutral (Alanine), acid (Glutamic acid) and basic (Lysine) amino acids [116]. Besides above
applications, the amino acids were good model to be used in investigate the basic partition
data, the influence factors, the extraction and the molecular level interactions behind the
extraction. In recent years, the amino acid ILs were studied in the extraction of chiral
separation of amino acids. For example, Tome et al. [12] took the amino acid L-tryptophan as
model biomolecule to make a detailed study of the chiral extraction and the factors in
extraction procedure above.

3.4.3. DNA
Deoxyribonucleic acid (DNA), the famous molecular in biology is a macromolecule
polymer. DNA is a very important bimolecular and fundamental ingredient of many
organisms, which can be used in several research areas. It can help study the life activity,
heredity and be used in authenticate. But all these must be done in what premise of separation
and purification. The degradation of DNA in extraction procedure must be avoided. The
isolation of double-stranded DNA by 1-butyl-3-methylimidazolium hexafluorophosphate was
showed here quoted from the reference [117]. The results showed that the ILs can
successfully avoid the degradation of DNA. Besides avoiding the degradation, they
successfully extracted DNA when the trace amounts of DNA was at the levels of <5 ng
microL-1. The two advantages above ensure the safety and effectiveness in the extraction of
DNA by using ILs, which was better than traditional organic solvents.

3.4.4. Biofuels and Biofeedstocks and Other Biomolecules

The range of biofuel and biofeedstocks is very wide. Methanol, ethanol, 1-propanol, 1-
butanol, and various other organic compounds can be produced biologically, and thus can be
considered as biofuel candidates, as biofeedstocks for production of other chemicals, and as
biobased solvents for various applications [118]. Conventional production of biofuels and
biofeedstocks were costly for the high cost of post processing energy. Because of the
advantageous characteristics of ILs,ILs as a potential extractant can be used in liquid-liquid
extraction of biofuel and biofeedstocks. For example, Simoni et al. [118] focused on the
extraction of 1-butanol from a dilute aqueous solution by ILs and successfully used 1-hexyl-
3-methylimidazolium bis(trifluoromethylsulfonyl)imide to extract it from water. Besides the
biomolecular mentioned above, extraction of other biomolecular by ILs were also studied
[119, 120]. Tzeng et al. [120] used a dye-modified IL to extract the lysozyme by employing
liquid-liquid extraction. ILs modified with other materials have also been summarized in
164 Yu Cao, Shun Yao, Xiaoming Wang, et al.

Tzeng’s paper. Young and co-workers [119] extracted bio-oils from biomass by the IL-polar
covalent molecule co-solvent systems. The ILs can handle different samples contained many
kinds of biomass. Huang et al. [121] extracted biogenic amines by IL-based ultrasonic-
assisted liquid-liquid microextraction method from beer samples.
The ILs have many advantages in the extraction of biological molecules as follows: 1.
ILs were thought as low or even no toxic solvent and they were suited in dealing with
products such as food and drugs related with human health; 2. It was thought the activity and
conformation of proteins can not be changed in extraction procedure; 3. ILs can handle
different samples in various kinds of environments; 4. The aftertreatment of ILextraction
technology was thought to be lower energy consumption and lower cost because of its unique
characteristics. With the development of ILs, it will be alternative to the organic solvent and
may be better than conventional extractants.

CONCLUSIONS
Conventional extraction with organic solvents or water has limitation or flaw for their
inherent drawbacks. As a kind of green solvent, ILs are used in extraction procedures by more
and more researchers due to its unique physical properties and application potential. Its
obvious advantages make it can not only be used in different kinds of targets and tasks, but
also can save the energy and reduce the cost in its recovery and post processing. The physical
and chemical properties of ILs related with extraction were reviewed in this article. ILs are
devisable solvents and their synthesis is not difficult. The summary of its properties about
extraction can give suggestions to the target synthesis of functional ILs which can be used in
separation and purification fields. The extraction of four typical kinds of molecules was
reviewed and new advances in these applications were also summarized. With the emergence
of more and more ILs, they will be applied in wider range in the near future.

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