26

Quaternary Ammonium and Phosphonium

Ionic Liquids in Chemical and
Environmental Engineering
Anja Stojanovic, Cornelia Morgenbesser, Daniel Kogelnig,
Regina Krachler and Bernhard K. Keppler
University of Vienna, Institute of Inorganic Chemistry,
Waehringer Straße 42, 1090 Vienna,
Austria

1. Introduction
Quaternary ammonium salts (quats) are an economically advantageous class of industrial
compounds. They have surface-active properties, possess anti-microbial activity and are
known to be bioactive (Boethling & Lynch, 1992; Juergensen et al., 2000). Contrary, reports
regarding low melting tetraalkylphosphonium salts were relatively rare in the literature
during the last decades (Bradaric et al., 2003).
Although ILs based on quaternary ammonium cations have been known and produced for
years, and also numerous phosphonium based ILs have been produced even in ton-scale,
these groups of ionic liquids have been more or less “neglected” in the literature comparing
to their imidazolium or pyridinium based counterparts. However, during the last decade
significant work has been done, pointing out the advantages and broad application
spectrum of these types of ionic liquids. Their improved thermal and chemical stability in
comparison to e.g. pyridinium and imidazolium based ILs, their unique miscibility
behaviour and solvating properties advances their use in specific applications (Rogers et al.,
2002; Plechkova & Seddon, 2007; Chowdhury et al., 2007; Wasserscheid & Welton, 2008).
Several ILs based on these classes of cations are already commercially available and have
been successfully applied as phase-transfer catalysts, solvents, lubricants, gas capture
agents, coating materials, or chemical sensors (Bradaric et al., 2003; Weng et al., 2006; Pernak
et al., 2006; Yuan et al., 2007; Fraser & MacFarlane, 2009; Werner et al., 2010).
Tricaprylylmethylammonium chloride (trade name Aliquat® 336), produced in ton-scale by
Henkel, is nowadays widely used as metal extraction agent, phase transfer catalyst,
surfactant, or antistatic agent. In contrast, trihexyl(tetradecyl)phosphonium chloride (trade
name Cyphos® IL 101) was developed by Cytec Industries as a thermally stable phase
transfer catalyst (Bradaric et al., 2003). Due to the relatively simple preparation route,
Cyphos® IL 101 is produced in ton-scale and therefore represents a fairly cheap IL. Hence,
due to their commercial availability and low prices, both Aliquat® 336 and Cyphos® IL 101
can be used themselves or represent favorable precursors for a series of ionic liquids. The
goal of this chapter is to give some insight into the fascinating and fast-growing field of

www.intechopen.com
658 Ionic Liquids: Theory, Properties, New Approaches

these groups of ILs - especially based on cations of the cost-saving precursors Aliquat® 336
and Cyphos® IL 101 – concerning the field of chemical and environmental engineering.

2. Synthesis of ammonium- and phosphonium-based ionic liquids

Aliquat® 336 ([A336][Cl]) is prepared by methylation of a mixture of trioctyl/decyl amine
(Alamine® 336, Cognis Corp.), whereas Cyphos® IL 101 ([P6,6,6,14][Cl]) is produced by Cytec
Ind. in a quaternization reaction of trihexylphosphine with 1-chlorotetradecane (Robertson,
2001; Bradaric et al., 2003). A subsequent anion-exchange reaction between the quaternary
ammonium/phosphonium halide and acid or salt (see Eqns. (1) and (2); R, R’ = alkyl; X =
halogen; M = alkali metal; A = desired anion) with corresponding anions leads to the
desired ionic liquid (Bradaric et al., 2003; Mikkola et al., 2006a; Kogelnig et al., 2008; Fraser &
MacFarlane, 2009).

[R’PR3]+[X]- + MA → [R’PR3]+[A]- + MX (1)

[R’NR3]+[X]- + HA + MOH→ [R’NR3]+[A]- + MX + H2O (2)

However, the cation generation by alkylation reaction with halides and the following anion
exchange often results in ILs comprising halide impurities, which results in alteration of their
physico-chemical properties (Seddon et al., 2000). As chloride impurities are for example
known to act as “catalytic poison”, ILs with halide contamination are unsuitable for catalytic
reactions (Davies et al., 2004). To overcome the drawback of halide impurities, many literature
protocols deal with synthetical approaches in which dialkylsulfates, carbonates,
trialkylphosphates, alkyltosylates, methane sulfonates or fluorined esters are used as
alkylating reagents (Bradaric et al., 2003; Seddon et al., 2001; Kalb, 2005). However, since the
main focus of this chapter lies on Aliquat® 336 and Cyphos® IL 101 based ionic liquids,
different metathesis routes including these two commercially available ILs as precursors will
be cited. Mikkola and co-workers (2006a) introduced the “new family” of ILs based on
Aliquat® 336 as cation source by conducting a simple metathesis route utilizing appropriate
sodium, potassium, or ammonium salts as anion source (see Eqn. 1). The authors obtained a
series of hydrophobic ILs containing common anions like [PF6]-, [BF4]-, phosphate, nitrate or
bis(trifluoromethylsulfonyl)imide ([Tf2N]-), but with a residual chloride content ranging
between 0 and 6 wt%. On the other hand, the use of economically favorable Aliquat® 336 as a
precursor may even justify the subsequent use of an anion exchanger in order to remove the
residual chloride content, if necessary for specific applications. A well-established example of
Eqn. (2) within the IL-community is the preparation of different phosphonium phosphinates
(Robertson & Seddon, 2002). Trihexyl(tetradecyl)phosphonium bis(2,4,4–
trimethylpentyl)phosphinate (trade name Cyphos® IL 104) is commercially produced
following this route (see Figure 1a, Bradaric et al., 2003). We also have shown recently
(Kogelnig et al., 2008) that the simple deprotonation-metathesis route (Eqn. 1) under inert
conditions leads to Aliquat-based ILs with sufficient purity (residual chloride contents
between <0.1 and 0.8 wt%) for selected applications (see Figure 1b).
The slightly modified synthesis route (Stojanovic et al., 2010) could also be applied for the
preparation of both ammonium- and phosphonium-based ILs containing functionalized
anions like thiosalicylate, 2-(methylthio)benzoate, or phenyl(thio)acetate. All prepared ILs
exhibited chloride contents below 0.9 wt.%. However, due to the significantly high
viscosities of the obtained ILs (up to 5242 mPas), the use of appropriate organic solvents was

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 659

Fig. 1. a) Synthesis of Cyphos® IL 104 (redrawn from Bradaric et al., 2003) b) Synthesis of
[P6,6,6,14] 2-methylthiobenzoate, [P6,6,6,14][MTBA] (redrawn from Stojanovic et al., 2010) c)
Acid/base neutralization synthesis route (redrawn from Sun et al., 2010a)
inevitable to minimize loss of yield, which makes the preparation process in general more
expensive and wasteful, limiting the industrial production of ILs. Sun et al. (2010a) recently
presented a relatively simple preparation strategy which may alleviate industrial
manufacturing of ammonium based ILs. Following the acid/base neutralization route
shown in Figure 1c, the authors gained the IL tricaprylylmethylammonium nitrate,
[A336][NO3], exhibiting a chloride content significantly lower than the same IL prepared via
the conventional anion metathesis route. Although the obtained IL still contains a
measurable amount of chloride, the described synthetic route may be attractive for large
scale preparation since its reactants are cheap and easily available in contrast to halide-free
intermediates.

3. Features of ammonium- and phosphonium-based ionic liquids

By now, numerous ILs based on both the Aliquat® 336 and the [P6,6,6,14] cation have been
prepared using one of the synthesis routes described above. Several selected examples of
common anions are presented in Figure 2.
The differences in physico-chemical properties of ammonium and phosphonium ILs begin
with their stability towards degradation under various conditions, which differs clearly
(Karodia et al., 1998; Wolff et al., 2000). Although both can decompose at elevated
temperatures, phosphonium salts are generally more stable as their ammonium analogs
(Wolff et al., 2000; Bradaric et al., 2003). Whereas ammonium salts undergo facile Hofmann-
or -eliminations in the presence of base (Hanhart & Ingold, 1927; Ingold & Vass, 1928),
their phosphonium analogs decompose to tertiary phosphine oxide and alkane under
alkaline conditions. Although the decomposition temperature of ILs depends strongly on
the choice of anion, in most cases thermogravimetric analysis (TGA) of phosphonium ILs
reveals a dynamic thermal stability even above 300°C (Bradaric et al., 2003; Fraser &
MacFarlane, 2009). In contrast, corresponding ammonium-based ILs decompose at
approximately 100°C lower temperatures. The enhanced thermal stability of phosphonium

www.intechopen.com
660 Ionic Liquids: Theory, Properties, New Approaches

Fig. 2. Selected anions of phosphonium- and ammonium-based ILs

ILs plays a crucial role when applied as solvents or catalysts for different reactions at high
temperatures, or if the reaction products should be distilled from the ionic liquid at high
temperatures. In general, the viscosity of Aliquat® 336-based ILs is significantly higher than
that of [P6,6,6,14] based ILs, but also strongly depends on the choice of anion. For example, the
exchange of the chloride anion with thiosalicylate leads to an increase in viscosity, whereas the
anion exchange with 2-(methylthio)benzoate leads to an increase in viscosity for the Aliquat®
336-based IL and to a decrease in viscosity for the corresponding phosphonium-based IL
(Stojanovic et al., 2010). However, due to the strong temperature dependence, viscosities
diminish extremely at temperatures typical for industrial applications (e.g. 70-100°C) (Bradaric
et al., 2003; Kulkarni et al., 2007a; Stojanovic et al., 2010). Furthermore, phosphonium ILs
generally depict higher electronic polarizabilities than their ammonium counterparts,
indicating a difference in their solvation behaviour (Tariq et al., 2009; Stojanovic et al., 2010),
whereas similarities can be found concerning the density. Both IL families exhibit densities
ranging from 0.7 to 1.2 g cm-3 with common values < 1 g cm-3. However, it is important to note
that a reliable set of data regarding physico-chemical parameters of ammonium and
phosphonium ILs is still missing, which limits their potential widespread industrial
application (Atkins et al., 2004). On the other hand, even the available data sets should be
considered carefully, since the properties of ILs strongly depend on their purity.
Besides an efficient and commercially favorable synthetic route, the determination of the
purity level of obtained ILs accompanied with their purification plays a crucial role for their
widespread use. Although the high-purity of ILs needs not to be achieved in every case,
several authors observed negative effects of halide and water impurities on the rate and/or
selectivity of reactions carried out in ionic liquids, on their catalytic performance as well as on
their properties (Carmichael et al., 1999; Seddon et al., 2000; Gallo et al., 2002; Davies et al.,
2004; Stark et al., 2006). From the engineering point of view, the presence of halide impurities
in ILs can influence the choice of constitutional materials due to the corrosiveness of these
anions. On the other hand, the presence of residual acid in ILs may have an impact on their
performance in catalytic and separation processes (Werner et al., 2010). It also has been shown
recently that the presence of impurities in ILs unambiguously narrows their apparent

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 661

electrochemical window, making the use of ultra high-purity ILs in electrochemical

applications necessary (Buzzeo et al., 2004). Besides conventional methods like NMR, IR, ESI-
MS, UV- spectroscopy, Karl-Fischer titration for the determination of water content, or
elemental analysis, only a few analytical methods are dealing with the characterization of
ammonium and phosphonium ILs. The absence of chromophoric UV-active groups in the
Aliquat® 336 and Cyphos® IL 101 cations makes the conventional RP-HPLC with UV-
detection unsuitable for these compounds, requesting more sophisticated coupling methods.
Moreover, several difficulties arise in the course of the analysis of Aliquat® 336-based ILs as
the cation depicts a mixture of quaternary ammonium cations with different alkyl chain
lengths rather than a well-defined pure compound. This property makes the quantification of
the Aliquat® 336 mix and hence all of its products more complicated. Lee et al. (1981)
identified Aliquat® 336 as a mixture of quaternary ammonium cations with C6, C8 and C10
alkyl chain lengths applying gas chromatography. The distinct composition of the Aliquat®
336 mix was confirmed and quantitatively determined via Electro Spray Mass Spectrometry
(ESMS), and revealed following mass percentages of different chloride components in
Aliquat® 336: 3.7 ± 0.7 % of methyl(n-hexyl)di(n-octyl)ammonium (A336+C23), 21.7 ± 1.5 % of
methyltri(n-octyl)ammonium (A336+C25), 32.8 ± 2.3 % of methyldi(n-octyl)(n-decyl)ammonium
(A336+C27), 18.4 ± 1.3 % of methyl(n-octyl)di(n-decyl)ammonium (A336+C29), and 3.5 ± 0.2 % of
methyltri(n-decyl)ammonium (A336+C31) (Argiropoulos et al., 1998b). Recently, we developed
an adequate, cost-saving and fast method for the purity determination of ammonium- and
phosphonium-based ILs (Stojanovic et al., 2008), applying Reversed Phase High Performance
Liquid Chromatography (RP-HPLC) with a serially coupled UV detector and a mass sensitive
charged aerosol detector (CAD). This combination allows a simultaneous quantitative
determination of non-chromophoric aliphatic cationic species and their aromatic, UV-active
anionic counterparts. Further, a unified calibration can be applied with a single standard. Most
notably, the resulting calibration function can be used for all other compounds or impurities
for which no standards are available – which is particularly suitable for mixtures like Aliquat®
336. As it can be seen in Figure 3, all five components of the Aliquat® 336 cation could be
efficiently separated and accurately quantified using an optimized step-gradient method,
confirming the results obtained by ESI-MS measurements. The developed method was
validated according to the ICH-guidelines (www.ich.org) and successfully applied for the
determination of molar ratios of ionic components of a series of Aliquat® 336- and Cyphos® IL
101-based ILs containing different aromatic anions.

Fig. 3. ESI-MS spectrum of Aliquat® 336 (left) and chromatogram of IL [A336][TS] (taken
from Stojanovic et al., 2008, Copyright © 2008 Elsevier B. V.)

www.intechopen.com
662 Ionic Liquids: Theory, Properties, New Approaches

4. Ammonium- and phosphonium-based ionic liquids in extraction processes

Due to the hydrophobicity of Aliquat® 336- and [P6,6,6,14]-based ILs the formation of liquid-
liquid biphasic systems with aqueous phases can be realized, making them suitable for such
extraction processes. On the other hand, due to their polar nature many ILs show a
pronounced miscibility gap with common apolar organic solvents. From the engineering
point of view a severe drawback of ILs compared to conventional solvents is based on their
high viscosity, requesting changes in the hydrodynamic design of extraction columns
(Meindersma et al, 2007). However, very little is known about the behaviour of ammonium
and phosphonium ILs in biphasic systems, e.g. about coalescence phenomena or micelle
formation etc. (Werner et al., 2010).

4.1 ILs as extracting agents for heavy metals

Already in the 1960`s Seeley & Crouse highlighted the enhanced performance of Aliquat®
336 as liquid ion-exchanger for the removal of different metal species from hydrochloric acid
solutions compared to conventionally used amine extractants like Alamine® 336 or
Amberlite LA-1 (Seeley & Crouse, 1966). Since then Aliquat® 336 has been evaluated as
extracting agent (in most cases dissolved in an appropriate organic solvent) for different
metals from acidic aqueous solutions (e.g. Cd(II), Fe(III), Pt(II) and Hg(II) from hydrochloric
acid solutions; El-Wakil et al., 1982; Hoh et al., 1985; de Mendonça Fábrega & Borges
Mansur, 2007). Nayl (2010) presented a successful separation of Co(II) and Ni(II) from acidic
sulfate solutions using Aliquat® 336 dissolved in kerosene. Further, Aliquat® 336 could be
efficiently applied for the recovery of Co and Ni from spent Ni-MH batteries (Nayl, 2010).
Aliquat® 336 dissolved in kerosene was also applied for the effective separation of Pt(IV)
from Rh(III) from acidic chloride solutions (Lee et al., 2009). As Aliquat® 336 was first applied
as extractant in the mining industry, it is not surprising that numerous studies are dealing with
the evaluation of its extraction ability towards uranium, thorium and several lanthanides (e.g.
Atanassova & Dukov, 2004; El-Nadi et al., 2005; Ali et al., 2007). In general, the extraction
mechanism with Aliquat® 336 is based on the anion exchange/ion association of metal
chloride/sulfate species; it therefore strongly depends on the composition of the aqueous
phase (formation of different metal species) and pH (see Eqns. 4 and 5). Hence, effective metal
stripping is mostly easily achieved by variation of pH, or via an efficient complexing agent like
thiourea. In contrast, Cyphos® IL 101 has only recently been investigated as potential new IL
extracting agent dissolved in toluene for the elimination of zinc and palladium from aqueous
phases (Regel-Rosocka, 2009; Cieszyńska et al., 2007). Alguacil and co-workers (2010)
investigated the transport of Cr (VI) through a pseudo-emulsion membrane from a feeding to
an appropriate stripping phase using Cyphos® IL 101 as metal carrier. Additionally, we have
investigated the separation of iron(III) and nickel(II) from hydrochloric acid solution (6 M HCl)
with Cyphos® IL 101 dissolved in chloroform (Kogelnig et al., 2010a). The efficient back
extraction was achieved with 0.5 M HCl solution. The conducted bulk liquid membrane (BLM)
experiments as well as kinetic model data elucidated the transport mechanism as a
combination of anion exchange and ion association (see Eqns. 4 and 5).

FeCl3 + PR4Cl → PR4 FeCl4 (4)

FeCl4 − + PR4Cl → PR4 FeCl4 + Cl − (5)

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 663

However, the application of Aliquat® 336 and Cyphos® IL 101 in liquid/liquid extraction
processes has several disadvantages. Firstly, due to the high viscosity of ILs the use of
organic solvents is inevitable, influencing both price and “greenness” of the process.
Secondly, the extraction mechanism is based on anion exchange and hence strongly
dependent on the composition of the aqueous phase. Further, the potential leachability of
both IL and organic solvent in the aqueous phase may pose an additional environmental
risk. Therefore, in order to overcome these drawbacks, two different approaches have been
developed during the last years: 1) Avoiding of liquid/liquid extraction and hence
increasing of the stability of the extracting agent may be achieved by immobilization of ILs
onto different solid materials or via embedment of ILs into different matrices. However, the
main challenge regarding these approaches is to attain the favorable performance of
“liquid” ionic liquids. 2) In order to avoid anion exchange and to enhance the extracting
ability, it is possible to combine favorable properties of quaternary ammonium and
phosphonium cations like hydrophobicity and thermal stability with different
functionalized anions containing functional moieties known for their affinity towards
selected metals, and forming task specific ionic liquids (TSILs) as metal scavengers.
Generally, problems connected with solvent extraction, like inhibition of phase separation
and product recovery by formation of difficult-to-separate emulsions, high consumption of
organic reagents, solvent loss or shortcomings due to the flooding and loading in
conventional column reactors may be overcome by so-called non dispersive solvent
extraction (Gabelman & Hwang, 1999). Thereby hollow fiber membranes or so-called
“supported liquid membranes” (SLMs), which consist of a porous polymeric (organic or
inorganic) material whose pores are impregnated or in contact with an extractant or carrier,
are used. Hollow fiber membranes impregnated with Aliquat® 336 as efficient ionic carrier
were evaluated for removal of different metal species, e.g. cobalt(III), rhodium(III), or
chromium(VI), from an aqueous feeding phase to an adequate stripping phase (Fontàs et
al., 2000; Kao & Juang, 2005; Güell et al., 2008). The hollow fiber liquid membrane using
Aliquat® 336 (35% v/v) as extractant and 0.5 M NaOH as stripping solution was successfully
applied for the removal of arsenic ions in waste water from a gas separation plant. The
extraction efficiency of Aliquat® 336 was thereby remarkably higher compared with other
evaluated extractants (Cyanex® 923, tri-n-butylphosphate (TBP), bis(2, 4, 4-trimethylpentyl)
dithiophosphinic acid (Cyanex® 301), tri-n-octylamine (TOA); Pancharoen et al., 2009).
Myasoedova et al. (2008) evaluated different solid supports (polyacetonitrile, Amberlite
XAD-7, hyper cross linked polystyrene or multi walled carbon nanotubes) with [P6,6,6,14][Cl],
[P6,6,6,14][PF6], and [P6,6,6,14][BF4] as solid-phase extractants for Pt(IV), U(VI) and Pu(IV) from
acid solutions, achieving the best performance with polyacrylonitrile impregnated with
Cyphos® IL 101. Next to SLMs, polymer inclusion membranes (PIMs) were evaluated as
solid supports for ILs. In contrast to SLMs, PIMs consist of a high molecular weight polymer
to provide mechanical strength, a plasticizer to provide elasticity and a carrier molecule for
facilitating the selective transport of the analytes (Nghiem et al., 2006). Polyvinyl chloride
(PVC) and cellulose triacetate (CTA) are the most commonly used polymers for the
preparation of PIMs, since they are able to embed carrier molecules and inhibit their
leaching. It is also noteworthy that the mechanical properties of PIMs are quite similar to
those of filtration membranes (Nghiem et al., 2006). Rahman and co-workers (2005) have
shown that ionic liquids could be used both as a carrier as well as a stable plasticizer for
PIMs. Until now, predominantly Aliquat® 336 has been evaluated as carrier for the
extraction of different metal species (e.g. Au(III) (Argiropoulos et al., 1998a), Cd(II), Cu(II)

www.intechopen.com
664 Ionic Liquids: Theory, Properties, New Approaches

(Wang et al., 2000), Co(II) (Blitz-Raith et al., 2007), Pd(II) (Kolev et al., 2000), and Zn(II) (Juang
et al., 2004)). Another interesting approach for the immobilization of ILs is the encapsulation of
liquid extractants in polystyrene microcapsules. Yang et al. (2005) investigated the uptake of
Cd(II), Cr(III), and Zn(II) from hydrochloric acid solutions by Aliquat® 336 encapsulated in
polystyrene particles. The encapsulated extractant displayed high stability over a wide pH-
range and the microcapsules could be successfully regenerated and reused several times,
hence justifying their relatively extensive preparation. Furthermore, Guibal et al. (2009)
selected another approach by choosing different biological materials such as alginate as
“green” materials for encapsulation or immobilization of extractants. The prepared alginate
particles were evaluated as efficient metal sorbents for Au(II), Hg(II), Pd(II), Pt(VI), or Bi(III)
from hydrochloric acid solutions. The disadvantages of the method, however, still originate
from the competition of metal ions capable of forming chloride complexes and the limitations
associated with slow mass transfer when using dried resins.
A further approach regarding the advancement of metal uptake ability of ILs is the use of
task specific ionic liquids as extracting agents. By anchoring different functional groups onto
the anion, it is possible to combine the hydrophobicity of ammonium and phosphonium
cations with the affinity of the functional group towards selected metal species, and hence
enhancing both efficiency and selectivity of the extracting agent. For example, an ionic
liquid based on the trioctylmethylammonium cation with thiosalicylate as anion, prepared
via a halide free synthesis route, is commercially available and has been evaluated as
extracting agent for heavy metals (e.g. Hg(II), Cu(II), or Pb(II)) from aqueous solutions with
high distribution coefficients (Kalb, 2005; Kalb et al., 2006).
By a simple anion exchange of the chloride anion of Aliquat® 336 with a salicylate anion,
Egorov et al. (2008, 2010) prepared a TSIL suitable for the extraction of Cu(II) and Fe(III)
from aqueous solutions. During the last years we have prepared a series of hydrophobic
ionic liquids based on Aliquat® 336- and [P6,6,6,14] cations with functionalized aromatic
anions (see Figure 2, Kogelnig et al., 2008; Stojanovic et al., 2010). The newly prepared IL
tricaprylylmethylammonium thiosalicylate, [A336][TS], could be evaluated as highly
effective extracting agent for Cd(II) from a natural river water matrix with a distribution
coefficient >104 (Kogelnig et al., 2008). The investigated IL exhibited high selectivity towards
cadmium in the presence of naturally occurring alkali and earth alkali metals (K+, Na+, Ca2+,
and Mg2+). The same IL was efficiently applied for the removal of uranium traces from
natural mineral water (Srncik et al., 2009). The selectivity of [A336][TS] towards alkali and
earth alkali metals and a subsequent successful stripping of uranium with 2 M HNO3 makes
this IL suitable as possible preconcentration agent for uranium for its subsequent analytical
determination in natural waters. Further, thiol- and thioether functionalized ILs ([A336][TS],
[P6,6,6,14][TS], [A336][MTBA], and [P6,6,6,14][MTBA]) seem to be suitable for the extraction of
Pt(II) from aqueous solutions (see Figure 4, Stojanovic et al., 2010). The incorporation of
aromatic anions significantly increased the stability of the investigated ILs in the aqueous
phase, whereby ILs containing [MTBA] exhibited an extremely high stability with a leaching
of the anion in the aqueous phase of max. 0.2 wt.%. Interestingly, the change from
ammonium to phosphonium cations for methylthiobenzoate and thiosalicylate
functionalized ILs resulted in different platinum uptake (see Figure 4). Whereas the highest
uptake of Pt(II) was achieved with [P6,6,6,14][MTBA], only 40% of Pt(II) could be extracted
with the ammonium analog. Therefore, also the physico-chemical properties of TSILs have
to be considered in order to determine distinct reaction mechanisms, as the presence of a
functional group is obviously not the sole factor influencing the extracting ability of TSILs.

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 665

Fig. 4. Extraction efficiency of [A336][TS], [A336][MTBA], [PR4][TS], and [PR4][MTBA] for

platinum(II) (Stojanovic et al., 2010, Copyright © CSIRO 2010)
A different concept of enhancing the extraction efficiency focuses on so-called bifunctional
ionic liquids (bif-ILs). The idea behind this concept is the synergetic effect on the solvent
extraction by combination of two extractants. An excellent example is given by the IL
[P6,6,6,14][bis(2,4,4-trimethylpentyl)phosphinate] (trade name Cyphos® IL 104), as displayed
in Figure 1a. In this case the synergetic effect on the solvent extraction is achieved by
combination of Cyphos® IL 101 and bis(2,4,4- trimethylpentyl)phosphonic acid, which is
known as excellent solvent for the extraction of cobalt and nickel from both hydrochloride
and sulfate acidic solutions (Rickelton et al., 1984; Danesi et al., 1985), and is currently used
to produce more than a half of the western world’s cobalt (Rickelton & Robertson, 1982;
Robertson, 1983; Rickelton et al., 1984). Sun et al. (2010b) investigated the separation of
cobalt and nickel by synergetic extraction with the Aliquat® 336-based bifunctional IL
[A336][CA-12] (see Figure 5). Their results indicated that the extraction abilities of the
tricaprylylmethylammonium cation ([A336]+) and the sec-octylphenoxy acetic acid group
([CA-12]-) can be remarkably enhanced by combining them in a corresponding IL. The same
authors also investigated the synergetic effect of different bifunctional ILs (see Figure 2) for
the extraction of europium and other rare earth elements from hydrochloric and nitric acid
media (Sun et al., 2010a). On the other hand, Liu et al. (2010) evaluated the bif-IL

Fig. 5. Extraction of cobalt with the ionic liquid [A336][CA-12] (redrawn from Sun et al., 2010b)

www.intechopen.com
666 Ionic Liquids: Theory, Properties, New Approaches

Cyphos® IL 104, together with soybean oil methyl ester (SBME, biodiesel) as delutant, as
extractant for rare earth elements from aqueous solutions. They achieved both enhanced
extracting efficiency due to the presence of the bif-ILE and a diminished loss of IL due to the
use of biodiesel as solvent.
In summary, the removal of heavy metals from aqueous solutions using phosphonium- and
ammonium-based ILs both as anion exchanger and as functionalized TSILs depicts a field of
extensive research and promising results. However, from the engineering and economic
point of view, extensive research is needed regarding a complete recovery of the ionic liquid
and the full isolation of the extracted metal from the loaded ionic liquid. Furthermore, the
question of ILs’ stability in aqueous phases and subsequently their possible toxicity towards
the aquatic environment still needs more attention.

4.2 Other separation processes with ammonium- and phosphonium-based ILs

Kulkarni et al. (2007b) investigated the absorption capacity of a series of Aliquat® 336-based
ILs (see Figure 2) towards organic vapors (1,4-benzodioxane, biphenyl, xylene, and
methanol) and received promising results with the ILs [A336][Tf2N] and [A336][DCA].
However, although both ILs showed remarkable absorption capacity, none of the tested ILs
was able to provide sufficient selectivity regarding different organic solutes (see Figure 6). A
possible solution may be a combination of different ILs in order to achieve the desired
selectivity. The absorbed organic solutes were recovered by desorption under vacuum and
preconcentrated by steam condensation. Compared to the relatively slow absorption
process, the organic vapors could be desorbed very fast (<12h). The recycled ILs were also
successfully reused. The same research group investigated the IL [A336][DCA] as capturing
agent for dioxins from the vapor phase (Kulkarni et al., 2008), whereby the investigated IL
absorbed 15.6 % by weight of dibenzo-p-dioxin in equilibrium. Due to the high thermal
stability of ammonium ILs, dioxin was easily desorbed by vacuum distillation at 100°C, and
the IL could be further reused.

Fig. 6. Extraction efficiency of Aliquat® 336-based ILs for organic vapors (taken from
Kulkarni et al., 2007b, Copyright© Wiley-VCH Verlag GmbH&Co. KgaA)

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 667

Furthermore, Egorov et al. (2008) investigated the extraction of eleven aromatic compounds
(phenols and aromatic amines) from aqueous phases with the Aliquat® 336-based IL
tricaprylylmethylammonium salicylate, [A336][Sal] (see Figure 2). The best results were
achieved for nitrophenols and naphtols, showing even better absorption capacities as
common imidazolium-based ILs over the investigated pH-range. Recently, Aliquat® 336 and
Cyphos® IL 101 were also evaluated as solvents for carboxylates and their extraction from
aqueous phase (Rosatella et al., 2009). Whereas a large quantity of disaccharide mixtures
was extracted, no satisfying extraction of monosaccharide mixtures was obtained. Further,
the highly hydrophobic IL trihexyl(tetradecyl)phosphonium
tris(pentafluoroethyl)trifluorophosphate, [PH3T][FAP], was evaluated as extraction agent
for polycyclic aromatic hydrocarbons from the aqueous phase via single drop
microextraction. Extremely high enrichment factors (680-2145) were achieved for
compounds with high molecular weights and fused rings (Yao et al., 2009). On the other
hand, Cyphos® IL 104 could be efficiently embedded in polysulfone resins and evaluated for
the extraction of phenol from aqueous solutions. Prepared polysulfone resins exhibit
remarkable mechanical stability and possess extremely high extractant loading capacity
(0.83-0.88 cm3g-1) (Van den Berg et al., 2009). Due to the favorable features of polysulfone
encapsuled ILs, this could be an interesting approach regarding the application of ILs in
separation processes.
Another interesting application field is the removal of carboxylic acids from aqueous
solutions. Both Aliquat® 336 and Cyphos® IL 101 have been investigated concerning their
extracting ability for several acids, e.g. lactic, levulinic, glutaric, or amino acids (e.g. Uddin
et al., 1990; Bora & Dutta, 1998; Kyuchoukov et al., 2005; Harington & Hossain, 2008;
Hossain & Maisuria, 2008; Uslu & Kırbaşlar, 2009; Pehlivanoğlu et al., 2010). As an
outstanding example the extraction of lactic acid with the bifunctionalized IL Cyphos® IL
104, should be mentioned. In contrast to distribution factors of about 1, which could be
reached with trialkylamines (e.g. trioctylamine) as classical lactic acid solvents, distribution
factors above 40 could be reached with Cyphos® IL 104. The assumed extraction mechanism
suggests the coordination of lactic acid (LA) to the IL under formation of complexes
(LAH)p(IL)(H2O)2 (with p ranging from 1-3). The uptake of LA by Cyphos® IL 104 is directly
connected with the water uptake of the IL, including the formation of reverse micelles in the
IL and inclusion of water into hydrated complexes of lactic acid (Marták & Schlosser, 2007).

5. Applications as catalysts and solvents in organic synthesis

Since the pioneering work of Mąkosza, Brändström, and Starks (Mąkosza & Serafinowa,
1965; Brändström & Gustavilii, 1969; Starks, 1971), quaternary ammonium and
phosphonium salts have been used as phase transfer catalysts in liquid/liquid biphasic
systems. Bender et al. (2010) evaluated a series of ILs including Aliquat® 336 as phase
transfer catalysts for the etherification reaction of 1-octanol with 1-chlorobutane. The
conversions ranged from 87-96% with Aliquat® 336 catalysts. Whereas the use of Aliquat 336
as a phase transfer catalyst is widespread and extensively investigated (e.g. Baidossi et al.,
1997; Villa et al., 2003; Rup et al., 2009), phosphonium ILs have only recently been
investigated for this application. Yadav & Tekale (2010) evaluated the ILs [P6,6,6,14][Cl],
[P6,6,6,14][Br], [P6,6,6,14][decanoate], and [P6,6,6,14][PF6] as phase transfer catalysts for selective O-
alkylation of 2-naphthol. Thereby, the reactivity of ILs was strongly dependent on the anion
attached to the phosphonium cation following the order Br- >Cl- > hexafluorophosphate >

www.intechopen.com
668 Ionic Liquids: Theory, Properties, New Approaches

decanoate, corresponding to the order of nucleophilicity for the anions. Hence, [P6,6,6,14][Br]
was chosen as most reactive catalyst. It depicted a good catalytic performance in the solid-
liquid phase transfer catalyzed synthesis of p-nitrodiphenyl ether, leading to 100%
selectivity towards the desired product (Yadav & Motirale, 2008).
Though Aliquat® 336 represents a widely used, economically favorable phase transfer
catalyst with remarkable performance, the main drawback is its chemical and thermal
stability. This could be overcome by the use of more stable phosphonium ILs, hence more
fundamental research should be done in this direction.
Regarding the environmental pressure to reduce waste and to reuse material in terms of
“green chemistry”, one of the most problematic areas to create environmentally friendly
solutions is the field of solution phase chemistry (Rogers et al., 2002; Fraser & MacFarlane,
2009). Phosphonium- and ammonium-based ILs may play a role in these efforts, as
described in following selected examples (Fraser & MacFarlane, 2009).
The Heck cross-coupling reaction is a common reaction for the formation of carbon-carbon
bonds between alkenes and organic halides (Heck & Nolley, 1972). Kaufmann et al. (1996)
applied a phosphonium-based IL, trihexyl(tetradecylphosphonium) bromide ([P6,6,6,14][Br],
trade name Cyphos® IL 162) as recyclable medium for the palladium-mediated Heck
coupling of aryl halides with acrylate esters (see Figure 7) for the first time. Although
relatively high yields were obtained, the reaction temperature was rather high (100°C) and
more activated aryl halides were strongly favored. In contrast, the use of Cyphos® IL 101
seems more applicative for Heck coupling reactions of deactivated and sterically demanding
aryl halides (see Figure 7). The reaction was conducted under moderate conditions (at 50°C
within 2h), resulting in sufficiently high yields (Gerritsma et al., 2004). Further evaluation of
different [P6,6,6,14]-based ILs revealed the dominant role of the chosen anion on the yield of
the reaction. Whereas ILs with chloride and decanoate anions seem to be suitable for high
yield Heck reactions, [PF6]- and [BF4]- containing ILs resulted in significantly lower yields
(Gerritsma et al., 2004). On the other hand, Aliquat® 336 was successfully applied as reaction
media for the palladium-catalyzed hydroxycarbonylation of aryl halides and benzyl
chloride derivatives (Mizushima et al., 2004), as its presence significantly enhanced the
hydroxycarbonylation reaction. Furthermore, the catalyst in the IL phase could be easily
recycled after extraction of the products with water.

Fig. 7. (a) [P6,6,6,14][Cl] ionic liquids reported as solvents in the Heck coupling reaction
(redrawn from Fraser & MacFarlane, 2009). (b) Suzuki coupling carried out in a
phosphonium ionic liquid (redrawn from Fraser & MacFarlane, 2009).

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 669

Several research groups investigated multiphase systems made by hydrogen, an aqueous

phase, isooctane, Aliquat® 336 as phase transfer agent and a heterogeneous catalyst (e.g.
Pd/C, Pt/C, Raney-Ni). These systems allow a variety of reduction reactions to be
conducted under mild conditions (T = 50°C, p(H2) = 1 atm), ranging from
hydrodehalogenation of aryl halides (Tundo et al., 2001; Marques et al., 1994, 1995),
hydrogenolysis of hydroxyls (Marques et al., 1995) up to aromatic hydrogenation (Marques
et al., 1995; Selva et al., 1998). Perosa et al. (2002) for example studied the multiphase
hydrogenolysis of benzyl methyl ether with different catalytic systems. It is noteworthy to
mention that the relatively inexpensive Raney-Ni system is effective for debenzylation
under such conditions while simpler systems require Pd/C as catalyst. This methodology
enables difficult transformations to be carried out under mild conditions, using a less
expensive catalytic system and allowing easy catalyst recovery and reuse. The same
working group observed a tenfold acceleration of a Heck coupling of aryl iodides with
electron poor olefins using a triphasic system containing Aliquat® 336 and Pd/C as catalyst
(Perosa et al., 2004).
Another interesting example is the use of ILs in Suzuki cross-coupling reactions (carbon-
carbon bond formation between an sp3 carbon or non- -hydride containing electrophile and
a boronic acid derivative; Miyaura & Suzuki, 1995). Cyphos® IL 101 has been recently
reported as an extremely successful medium for such types of reaction (see Figure 7,
McNulty et al., 2002). The palladium catalyst (Pd2(dba)3CHCl3) was dissolved in the IL,
forming a stable solution in absence of oxygen, and hence could also be effectively recycled
after solvent extraction of reaction products. The Suzuki reactions in Cyphos® IL 101 were
efficient even under moderate conditions (50-70°C), whereas the use of imidazolium-based
ILs in contrast requires elevated temperatures (up to 110°C) (Mathews et al., 2000).
In general, ILs are also regarded as favorable solvents for Diels-Alder reactions, producing
good to high yields (Welton, 1999). Janus & Stefaniak (2008) reported that Diels-Alder
reactions carried out in the phosphonium IL [P6,6,6,14][Tf2N] under presence of catalysts
occurs smoothly, in short time and with high yield and high stereoselectivity. Further
advantages of the reaction originate from the good solubility of catalysts belonging to the
group of metal chlorides, triflates, and bis-triflimides in [P6,6,6,14][Tf2N] and - due to the high
thermal stability of the IL - from the easy separation of the product via distillation. Several
authors have been investigating the use of phosphonium-based ILs as media for strong base
mediated reactions such as Grignard reactions (Ramnial et al., 2005; Law et al., 2006; Fraser
& MacFarlane, 2009). Ramnial et al. (2008) investigated the ILs Cyphos® IL 101 and
trihexyl(tetradecyl)phosphonium decanoate, [P6,6,6,14][C9H19COO], as solvents for bases such
as Grignard reagents, isocyanides, Wittig reagents (phosphoranes), and N-heterocyclic
carbenes. The authors illustrated that ILs can be used for generating N-heterocyclic carbenes
and their metal complexes and as solvent medium for the generation of Wittig reagents. The
reactivity of Cyphos® IL 101 in Grignard reagent solutions with tetrahydrofuran-to-IL ratio
of 1:3 was tested by the addition of anhydrous bromine resulting in the exclusive formation
of bromobenzene. Furthermore, Cyphos® IL 101 seems to be stable in basic Grignard
reagents solutions, since even after one month no deprotonation was observed (Ramnial et
al., 2008). It should also be noted that the use of phosphonium-based ILs facilitates the
separation of the product due to the formation of three-phasic systems of some
IL/water/hexane combinations. This may reduce the use of ethereal solvents in this class of
reactions and hence lead to a general “greening” of Grignard chemistry (Ramnial et al., 2005;
Fraser & MacFarlane, 2009). However, phosphonium-based ILs may also undergo

www.intechopen.com
670 Ionic Liquids: Theory, Properties, New Approaches

deprotonation in the presence of strong base, similarly to the C-H activation of imidazolium
based ILs (Fraser & MacFarlane, 2009). Tseng et al. (2007) clearly indicated that the -protons
of [P6,6,6,14] ions, although shielded, are still accessible to small bases such as OH-. However,
this exchange does not seem to produce a significant impact on the acidity of the cation.
Another promising field of phosphonium and ammonium ILs comprises the metal based
ionic liquids. Following the idea of Hayashi and co-workers (Hayashi & Hamaguchi, 2004;
Hayashi et al., 2006; Okuno & Hamaguchi, 2006). Del Sesto et al. (2008) prepared a set of
transition metal based [P6,6,6,14]-ILs. The simple reaction of Cyphos® IL 101 with FeCl3, CoCl3,
MnCl2 or GdCl3 yields the corresponding ILs. All prepared ILs exhibited paramagnetic
behavior as a sole property of ILs, and hence a series of hydrophobic, magnetic ILs was
prepared. We have recently shown that the reaction of Aliquat® 336 with FeCl3 leads to the
corresponding paramagnetic IL tricaprylylmethylammonium tetrachloroferrate,
[A336][FeCl4] (Kogelnig et al., 2010b). The development of magnetic ILs opens a new field of
possible applications (e.g. as catalysts, Bica and Gaertner, 2006; Nguyen et al., 2008).
One more aspect is worth mentioning regarding possible applications of ammonium and
phosphonium ILs in environmental and chemical engineering: the environmental impact.
Although ILs were often described as new „environmental benign“ and „green“ compounds
due to their low (often immeasurable) vapor pressure and non-inflammability, many new
ILs have shown to be toxic (e.g.) to aquatic organisms, or even explosive (Pham et al., 2010;
Gao et al., 2009). In general, very little is known about the toxicity of ammonium and
phosphonium ILs. Frade et al. (2009) investigated the toxicity of selected ILs in a human
colon carcinoma cell line (CaCo-2). The evaluated Aliquat® 336-based ILs
[A336][Cl]/[FeCl4]/[TFA]/[TfO] are very toxic and can not be regarded as candidates for
greener solvents. Interestingly, whereas [P6,6,6,14][Cl]/[FeCl4] were also very toxic, the
dicyanamide ([DCA]) anion led to a considerable decrease in toxicity. Kumar & Molhotra
(2009) investigated the potential anti-cancer activity and cytotoxicity of selected ammonium-
and phosphonium-based ILs. Cyphos® IL 101 may also be regarded as toxic in aquatic
environment, exhibiting much higher ecotoxicity compared with common organic solvents
(Wells & Coombe, 2006). The activity and cytotoxicity of investigated ILs were strongly
influenced by alkyl chain length of and alkyl substitution on the cations. In general,
phosphonium ILs were more active and less cytotoxic compared with ammonium ILs.
Hence, ammonium and phosphonium ILs should not be a priori regarded as “green”
solvents, and their behavior and environmental impact has to be extensively studied.

6. Conclusions
Ammonium and phosphonium ionic liquids undoubtedly represent a promising group of
ILs. However, as it can be seen in examples presented in previous sections, many of the
discussed applications and concepts are still in the early stage of development (with the
exception of several widespread applications of Aliquat® 336, of course). This can be
attributed mainly to the circumstance that ammonium- and phosphonium-based ILs have
just recently gained attention both in the ionic liquid and engineering community. Hence
most of the examples presented in the literature still deal with concept research. On the
other hand the development of engineering applications of ILs generally requires a reliable
and broad spectrum of knowledge concerning the nature of the IL itself and of relevant
aspects regarding the attended application. At current stage of research much more
information concerning fundamental IL properties and behavior is needed. In the further

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 671

stage of development aspects like efficiency of the recycling process, ionic liquid recovery
and reusability, or the degree of ionic liquid degradation with time needs to be considered.
Further, the toxicity and environmental impact of this group of ILs needs to be extensively
studied as both Aliquat® 336 and Cyphos® IL 101 can not be regarded as “green” solvents.

7. References
Alguacil, F. J., Alonso, M., Lopez, F. A. & Lopez-Delgado, A. (2010). Pseudo-emulsion
membrane strip dispersion (PEMSD) pertraction of chromium(VI) using Cyphos IL
101 ionic liquid as carrier. Environmental Science and Technology, in press, DOI:
10.1021/es101302b
Ali, A. M. I., El-Nadi, Y. A., Daoud, J. A. & Aly, H. F. (2007). Recovery of thorium (IV) from
leached monazite solutions using counter-current extraction. International Journal of
Mineral Processing, 81, 4, 217-223, ISSN: 0301-7516
Argiropoulos, G., Cattrall, R. W., Hamilton, I. C., Kolev, S. D. & Paimin, R. (1998a). The
study of a membrane for extracting gold(III) from hydrochloric acid solutions.
Journal of Membrane Science, 138, 2, 279-285, ISSN: 0376-7388
Argiropoulos, G., Cattrall, R. W., Hamilton, I. C. & Paimin, R. (1998b). Determination of the
quaternary ammonium ion components of Aliquat 336 by electrospray mass
spectrometry. Analytica Chimica Acta, 360, 1-3, 167-169, ISSN: 0003-2670
Atkins, M.P., Davey, P., Fitzwater, G., Rouher, O., Seddon, K.R. & Swindall, J. (2004). Ionic
Liquids: A Map for Industrial Innovation. Report Q001, January 2004, QUILL, Belfast
Atanassova, M. & Dukov, I. L. (2004). Synergistic solvent extraction and separation of
trivalent lanthanide metals with mixtures of 4-benzoyl-3-methyl-1-phenyl-2-
pyrazolin-5-one and Aliquat 336. Separation and Purification Technology, 40, 2, 171-
176, ISSN: 1383-5866
Baidossi, W., Lahav, M. & Blum, J. (1997). Hydration of alkynes by a PtCl4−CO catalyst.
Journal of Organic Chemistry, 62, 3, 669-672, ISSN: 0022-3263
Bender, J., Jepkens, D. & Hüsken, H. (2010). Ionic liquids as phase-transfer catalysts:
Etherification reaction of 1-Octanol with 1-Chlorobutane. Organic Process Research &
Development, 14, 3, 716-721, ISSN: 1083-6160
Bica, K. & Gaertner, P. (2006). An iron containing ionic liquid as recyclable catalyst for aryl
Grignard cross-coupling of alkyl halides. Organic Letters, 8, 4, 733-735, ISSN: 1523-
7060
Blitz-Raith, A. H., Paimin, R., Cattrall, R. W. & Kolev, S. D. (2007). Separation of cobalt(II)
from nickel(II) by solid-phase extraction into Aliquat 336 chloride immobilized in
poly(vinyl chloride). Talanta, 71, 1, 419-423, ISSN: 0039-9140
Boethling, R. S. & Lynch, D. G. (1992). Quaternary ammonium surfactants, In: The Handbook
of Environmental Chemistry, Oude, N. T. (Ed.), 3, 144-177, Springer, ISSN 1867-979X,
Berlin, Germany
Bora, M. M. & Dutta, N. N. (1998). Extraction of 7-aminocephalosporanic acid with
secondary, tertiary, and quaternary amines. Journal of Chemical and Engineering Data,
43, 3, 318-324, ISSN: 0021-9568

www.intechopen.com
672 Ionic Liquids: Theory, Properties, New Approaches

Bradaric, C. J., Downard, A., Kennedy, C., Robertson, A. J. & Zhou, Y. (2003). Industrial
preparation of phosphonium ionic liquids. Green Chemistry, 5, 2, 143-152, ISSN:
1463-9262
Brändström, A. & Gustavii, K. (1969). Ion pair extraction in preparative organic chemistry.
Acta Chemica Scandinavica, 23, 4, 1215-1218, ISSN: 0001-5393
Buzzeo, M. C., Evans, R. G. & Compton, R. G. (2004). Non-haloaluminate room-temperature
ionic liquids in electrochemistry - a review. ChemPhysChem, 5, 8, 1106-1120, ISSN:
1439-4235
Carmichael, A. J., Earle, M. J., Holbrey, J. D., McCormac, P. B. & Seddon, K. R. (1999). The
Heck reaction in ionic liquids: A multiphasic catalyst system. Organic Letters, 1, 7,
997-1000, ISSN: 1523-7060
Chowdhury, S., Mohan, R. S. & Scott, J. L. (2007). Reactivity of ionic liquids. Tetrahedron, 63,
11, 2363-2389, ISSN: 0040-4020
Cieszyńska, A., Regel-Rosocka, M. & Wiśniewski, M. (2007). Extraction of palladium(II) ions
from chloride solutions with phosphonium ionic liquid Cyphos® IL 101. Polish
Journal of Chemical Technology, 9, 2, 99-101, ISSN: 1509-8117
Danesi, P. R., Reichley-Yinger, L., Mason, G., Kaplan, L., Horwitz, E. P. & Diamond, H.
(1985). Selectivity-structure trends in the extraction of cobalt(II) and nickel(II) by
dialkyl phosphoric, alkyl alkylphosphonic, and dialkylphosphinic acids. Solvent
Extraction and Ion Exchange, 3, 4, 135-452, ISSN: 0736-6399
Davies, D. L., Kandola, S. K. & Patel, R. K. (2004). Asymmetric cyclopropanation in ionic
liquids: effect of anion and impurities. Tetrahedron: Asymmetry, 15, 1, 77-80, ISSN:
0957-4166
Del Sesto, R. E., McCleskey, T. M., Burrell, A. K., Baker, G. A., Thompson, J. D., Scott, B. L.,
Wilkes, J. S. & Williams, P. (2008). Structure and magnetic behavior of transition
metal based ionic liquids. Chemical Communications, 447-449, ISSN: 1359-7345
De Mendonça Fábrega, F. & Borges Mansur, M. (2007). Liquid-liquid extraction of
mercury(II) from hydrochloric acid solutions by Aliquat 336. Hydrometallurgy, 87, 3-
4, 83-90, ISSN: 0304-386X
Egorov, V. M., Smirnova, S. V. & Pletnev, I. V. (2008). Highly efficient extraction of phenols
and aromatic amines into novel ionic liquids incorporating quaternary ammonium
cation. Separation and Purification Technology, 63, 3, 710-715, ISSN: 1383-5866
Egorov, V. M., Djigailo, D. I., Momotenko, D. S., Chernyshov, D. V., Torocheshnikova, I. I.,
Smirnova, S. V. & Pletnev, I. V. (2010). Task-specific ionic liquid
trioctylmethylammonium salicylate as extraction solvent for transition metal ions.
Talanta, 80, 3, 1177-1182, ISSN: 0039-9140
El-Nadi, Y. A., Daoud, J. A. & Aly, H. F. (2005). Modified leaching and extraction of uranium
from hydrous oxide cake of Egyptian monazite. International Journal of Mineral
Processing, 76, 1-2, 101-110, ISSN: 0301-7516
El-Wakil, A. M., Farag, A. B. & Ez-Eldin, A. K. (1982). Liquid-liquid extraction of iron(III),
cobalt(II), nickel(II) and cadmium(II) from aqueous halide media with Aliquat 336.
Fresenius’ Zeitschrift für Analalytische Chemie, 311, 5, 522-526, ISSN: 0016-1152

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 673

Fontàs, C., Palet, C., Salvado, V. & Hidalgo, M. (2000). A hollow fiber supported liquid
membrane based on Aliquat 336 as a carrier for rhodium(III) transport and
preconcentration. Journal of Membrane Science, 178, 1-2, 131-139, ISSN: 0376-7388
Frade, R. F. M., Rosatella, A. A., Marques, C. S., Branco, L. C., Kulkarni, P. S., Mateus, N. M.
M., Afonso, C. A. M. & Duarte, C. M. M. (2009). Toxicological evaluation on human
colon carcinoma cell line (CaCo-2) of ionic liquids based on imidazolium,
guanidinium, ammonium, phosphonium, pyridinium and pyrrolidinium cations.
Green Chemistry, 11, 10, 1660-1665, ISSN: 1463-9262
Fraser K. J. & MacFarlane D. R. (2009). Phosphonium-based ionic liquids: An overview.
Australian Journal of Chemistry, 62, 4, 309-321, ISSN: 0004-9425
Gabelman, A. & Hwang, S.-T. (1999). Hollow fiber membrane contactors. Journal of
Membrane Science, 159, 1-2, 61-106, ISSN: 0376-7388
Gallo, V., Mastrorilli, P., Nobile, C. F., Romanazzi, G. & Suranna, G. P. (2002). How does the
presence of impurities change the performance of catalytic systems in ionic liquids?
A case study: the Michael addition of acetylacetone to methyl vinyl ketone. Journal
of the Chemical Society, Dalton Transactions, 23, 4339-4342, ISSN: 1472-7773
Gao, H., Joo, Y.-H., Twamley, B., Zhou, Z. & Shreeve, J. M. (2009). Hypergolic ionic liquids
with the 2,2-dialkyltriazanium cation. Angewandte Chemie, International Edition, 48,
15, 2792-2795, ISSN: 1433-7851
Gerritsma, D. A., Robertson, A., McNulty, J. & Capretta, A. (2004). Heck reactions of aryl
halides in phosphonium salt ionic liquids: library screening and applications.
Tetrahedron Letters, 45, 41, 7629-7631, ISSN: 0040-4039
Güell, R., Antico, E., Salvado, V. & Fontàs, C. (2008). Efficient hollow fiber supported liquid
membrane system for the removal and preconcentration of Cr(VI) at trace levels.
Separation and Purification Technology, 62, 2, 389-393, ISSN: 1383-5866
Guibal, E., Vincent, T. & Jouannin, C. (2009). Immobilization of extractants in biopolymer
capsules for the synthesis of new resins: a focus on the encapsulation of tetraalkyl
phosphonium ionic liquids. Journal of Materials Chemistry, 19, 45, 8515-8527, ISSN:
0959-9428
Hanhart, W. & Ingold, C. K. (1927). Nature of the alternating effect in carbon chains. XVIII.
Mechanism of exhaustive methylation and its relation to anomalous hydrolysis.
Journal of the Chemical Society, 997-1020, ISSN: 0368-1769
Harington, T. & Hossain, Md. M. (2008). Extraction of lactic acid into sunflower oil and its
recovery into an aqueous solution. Desalination, 218, 1-3, 287-296, ISSN: 0011-9164
Hayashi, S. & Hamaguchi, H. (2004). Discovery of a magnetic ionic liquid [bmim]FeCl4.
Chemistry Letters, 33, 12, 1590-1591, ISSN: 00366-7022
Hayashi, S., Saha, S. & Hamaguchi, H. (2006). A new class of magnetic fluids: bmim[FeCl4]
and nbmim[FeCl4] ionic liquids. IEEE Transactions on Magnetics, 42, 1, 12-14, ISSN:
0018-9464
Heck, R. F. & Nolley, J. P. Jr. (1972). Palladium-catalyzed vinylic substitution reactions with
aryl, benzyl, and styryl halides. Journal of Organic Chemistry, 37, 14, 2320-2322, ISSN:
0022-3263

www.intechopen.com
674 Ionic Liquids: Theory, Properties, New Approaches

Hoh, Y. C., Chuang, W. S. & Yueh, P. S. (1985). The extraction of platinum from platinum(II)
chloride solution by a quaternary ammonium compound. Journal of Chemical
Technology and Biotechnology, Chemical Technology, 35A, 1, 41-47, ISSN: 0264-3413
Hossain, Md. M. & Maisuria, J. L. (2008). Effects of organic phase, fermentation media, and
operating conditions on lactic acid extraction. Biotechnology Progress, 24, 3, 757-765,
ISSN: 8156-7938
http://www.ich.org
http://www.cognis.com
Ingold, C. K. & Vass, C. C. N. (1928). The influence of poles and polar linkings on the course
pursued by elimination reactions II. The mechanism of exhaustive methylation.
Journal of the Chemical Society, 3125-3127, ISSN: 0368-1769
Janus, E. & Stefaniak, W. (2008). The Diels-Alder reaction in phosphonium ionic liquid
catalysed by metal chlorides, triflates and triflimides. Catalysis Letters, 124, 1-2, 105-
110, ISSN: 1011-372X
Juang, R.-S., Kao, H.-C. & Wu, W.-H. (2004). Analysis of liquid membrane extraction of
binary Zn(II) and Cd(II) from chloride media with Aliquat 336 based on
thermodynamic equilibrium models. Journal of Membrane Science, 228, 2, 169-177,
ISSN: 0376-7388
Juergensen, L., Busnarda, J., Caux, P. Y. & Kent, R. A. (2000). Fate, behaviour, and aquatic
toxicity of the fungicide DDAC in the Canadian environment. Environmental
Toxicology, 15, 3, 174-200, ISSN: 1520-4081
Kalb, R. S. (2005). Method for producing ionic liquids, ionic solids or mixtures thereof. WO
2005 021484.
Kalb, R. S., Krachler, R. & Keppler, B. K. (2006). Determination of heavy metal polluted
process water, waste water and filter cake with high performance. Chemical Industry
and Environment V, Volume I, W. Höflinger (Ed.), EMChIE, Vienna, Austria.
Kao, H.-C. & Juang, R.-S. (2005). Kinetic analysis of non-dispersive solvent extraction of
concentrated Co(II) from chloride solutions with Aliquat 336: Significance of the
knowledge of reaction equilibrium. Journal of Membrane Science, 264, 1-2, 104–112,
ISSN: 0376-7388
Karodia, N., Guise, S., Newlands, C. & Andersen, J. (1998). Clean catalysis with ionic
solvents - phosphonium tosylates for hydroformylation. Chemical Communications,
21, 2341-2342, ISSN: 1359-7345
Kaufmann, D. E., Nouroozian, M. & Henze, H. (1996). Molten salts as an efficient medium
for palladium-catalyzed C-C coupling reactions. Synlett, 11, 1091-1092, ISSN: 0936-
5214
Kogelnig, D., Stojanovic, A., Galanski, M., Grössl, M., Jirsa, F., Krachler, R. & Keppler, B. K.
(2008). Greener synthesis of new ammonium ionic liquids and their potential as
extracting agents. Tetrahedron Letters, 49, 17, 2782–2785, ISSN: 0040-4039
Kogelnig, D., Stojanovic, A., Jirsa, F., Körner, W., Krachler, R. & Keppler, B. K. (2010a).
Transport and separation of iron(III) from nickel(II) with the ionic liquid
trihexyl(tetradecyl)phosphonium chloride. Separation and Purification Technology, 72,
1, 56–60, ISSN: 1383-5866

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 675

Kogelnig, D., Stojanovic, A., Kammer, F. v. d., Terzieff, P., Galanski, M., Krachler, R. &
Keppler, B. K. (2010b). Tricaprylylmethylammonium tetrachloroferrate ionic liquid:
magnetic- and aggregation behavior. Inorganic Chemistry Communications, 13, 12,
1485-1488, ISSN: 1387-7003
Kolev, S. D., Sakai, Y., Cattrall, R. W., Paimin, R. & Potter, I. D. (2000). Theoretical and
experimental study of palladium(II) extraction from hydrochloric acid solutions
into Aliquat 336/PVC membranes. Analytica Chimica Acta, 413, 1-2, 241-246, ISSN:
0003-2670
Kulkarni, P. S., Branco, L. C., Crespo, J. G., Nunes, M. C., Raymundo, A. & Afonso, C. A. M.
(2007a). Comparison of physicochemical properties of new ionic liquids based on
imidazolium, quaternary ammonium, and guanidinium cations. Chemistry – A
European Journal, 13, 30, 8478-8488, ISSN: 0947-6539
Kulkarni, P. S., Branco, L. C., Crespo, J. G. & Afonso, C. A. M. (2007b). A comparative study
on absorption and selectivity of organic vapors by using ionic liquids based on
imidazolium, quaternary ammonium, and guanidinium cations. Chemistry – A
European Journal, 13, 30, 8470-8477, ISSN: 0947-6539
Kulkarni, P. S., Branco, L. C., Crespo, J. G. & Afonso, C. A. M. (2008). Capture of dioxins by
ionic liquids. Environmental Science & Technology, 42, 7, 2570-2574, ISSN: 0013-936X
Kumar, V. & Malhotra, S. V. (2009). Study on the potential anti-cancer activity of
phosphonium and ammonium-based ionic liquids. Bioorganic & Medicinal Chemistry
Letters, 19, 16, 4643-4646, ISSN: 0960-894X
Kyuchoukov, G., Yankov, D., Albet, J. & Molinier, J. (2005). Mechanism of lactic acid
extraction with quaternary ammonium chloride (Aliquat 336). Industrial &
Engineering Chemistry Research, 44, 15, 5733-5739, ISSN: 6534-6538
Law, M. C., Wong, K.-Y. & Chan, T. H. (2006). Grignard reagents in ionic liquids. Chemical
Communications, 23, 2457-2459, ISSN: 1359-7345
Lee, G. L., Cattrall, R. W., Daud, H. & Smith, J. F. (1981). The analysis of aliquat-336 by gas
chromatography. Analytica Chimica Acta, 123, 213-220, ISSN: 0003-2670
Lee, J.-Y., Kumar, R. J., Kim, J.-S., Kim, D.-J. & Yoon, H.-S. (2009). Extraction and separation
of Pt(IV)/Rh(III) from acidic chloride solutions using Aliquat 336. Journal of
Industrial and Engineering Chemistry, 15, 3, 359-364, ISSN: 1226-086X
Liu, Y., Zhu, L., Sun, X. & Chen, L. (2010). Toward greener separations of rare earths:
bifunctional ionic liquid extractants in biodiesel. AIChE Journal, 56, 9, 2338-2346,
ISSN: 0001-1541
Mąkosza, M. & Serafinowa, B. (1965). Reactions of organic anions. Part I. Catalytic ethylation
of phenylacetonitrile in aqueous medium. Roczniki Chemii, 39, 9, 1223-1231, ISSN:
0035-7677
Marques, C. A., Selva, M. & Tundo, P. (1994). Facile hydrodehalogenation with H2 and
Pd/C catalyst under multiphase conditions 2. Selectivity and kinetics. Journal of
Organic Chemistry, 59, 14, 3830-3837, ISSN: 0022-3263
Marques, C. A., Selva, M. & Tundo, P. (1995). Facile hydrohalogenation with H2 and Pd/C
catalyst under multiphase conditions 3. Selective removal of halogen from
functionalized aryl ketones. 4. Aryl halide-promoted reduction of benzyl alcohols
to alkanes. Journal of Organic Chemistry, 60, 8, 2430-2435, ISSN: 0022-3263

www.intechopen.com
676 Ionic Liquids: Theory, Properties, New Approaches

Marták, J. & Schlosser, S. (2007). Extraction of lactic acid by phosphonium ionic liquids.
Separation and Purification Technology, 57, 3, 483-494, ISSN: 1383-5866
Mathews, C. J., Smith, P. J. & Welton, T. (2000). Palladium catalyzed Suzuki cross-coupling
reactions in ambient temperature ionic liquids. Chemical Communications, 14, 1249-
1250, ISSN: 1359-7345
McNulty, J., Capretta, A., Wilson, J., Dyck, J., Adjabeng, G. & Robertson, A. (2002). Suzuki
cross-coupling reactions of aryl halides in phosphonium salt ionic liquid under
mild conditions. Chemical Communications, 17, 1986-1987, ISSN : 1359-7345
Meindersma, G. W., Galán Sánchez, L. M., Hansmeier, A. R. & de Haan, A. B. (2007).
Application of task-specific ionic liquids for intensified separations. Monatshefte für
Chemie, 138, 11, 1125–1136, ISSN: 0026-9247
Mikkola, J.-P., Virtanen, P. & Sjöholm., R. (2006a). Aliquat 336®—a versatile and affordable
cation source for an entirely new family of hydrophobic ionic liquids. Green
Chemistry, 8, 250-255, ISSN: 1463-9262
Mizushima, E., Hayashi, T. & Tanaka, M. (2004). Environmentally benign carbonylation
reaction: palladium-catalyzed hydroxycarbonylation of aryl halides and benzyl
chloride derivatives in ionic liquid media. Topics in Catalysis, 29, 3-4, ISSN: 1022-
5528
Miyaura, N. & Suzuki, A. (1995). Palladium-catalyzed cross-coupling reactions of
organoboron compounds. Chemical Reviews, 95, 7, 2457-2483, ISSN: 0009-2665
Myasoedova, G. V., Molochnikova, N. P., Mokhodoeva, O. B. & Myasoedov, B. F. (2008).
Application of ionic liquids for solid-phase extraction of trace elements. Analytical
Sciences, 24, 10, 1351-1353, ISSN: 0910-6340
Nayl, A. A. (2010). Extraction and separation of Co(II) and Ni(II) from acidic sulfate
solutions using Aliquat 336. Journal of Hazardous Materials, 173, 1-3, 223-230, ISSN:
0304-3894
Nghiem, L. D., Mornane, P., Potter, I. D., Perera, J. M., Cattrall, R. W. & Kolev, S. D. (2006).
Extraction and transport of metal ions and small organic compounds using
polymer inclusion membranes (PIMs). Journal of Membrane Science, 281, 1+2, 7-41,
ISSN: 0376-7388
Nguyen, M. D., Nguyen, L. V., Jeon, E. H., Kim, J. H., Cheong, M., Kim, H. S. & Lee, J. S.
(2008). Fe-containing ionic liquids as catalysts for the dimerization of
bicycle[2.2.1]hepta-2,5-diene. Journal of Catalysis, 258, 1, 5-13, ISSN: 0021-9517
Okuno, M., Hamaguchi, H. & Hayashi, S. (2006). Magnetic manipulation of materials in a
magnetic ionic liquid. Applied Physics Letters, 89, 13, 132506/1-2, ISSN: 0003-6951
Pancharoen, U., Poonkum, W. & Lothongkum, A.W. (2009). Treatment of arsenic ions from
produced water through hollow fiber supported liquid membrane. Journal of Alloys
and Compounds, 482, 1-2, 328-334, ISSN: 0925-8388
Pernak, J., Smiglak, M., Griffin, S. T., Hough, W. L., Wilson, T. B., Pernak, A., Zabielska-
Matejuk, J., Fojutowski, A., Kita, K. & Rogers, R. D. (2006). Long alkyl chain
quaternary ammonium-based ionic liquids and potential applications. Green
Chemistry, 8, 9, 798 – 806, ISSN: 1463-9262
Perosa, A., Tundo, P. & Zinovyev, S. (2002). Mild catalytic multiphase hydrogenolysis of
benzyl ethers. Green Chemistry, 4, 5, 492-494, ISSN: 1463-9262

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 677

Perosa, A., Tundo, P., Selva, M., Zinovyev, S. & Testa, A. (2004). Heck reaction catalyzed by
Pd/C, in a triphasic-organic/Aliquat 336/aqueous-solvent system. Organic &
Biomolecular Chemistry, 2, 15, 2249-2252, ISSN: 1477-0520
Pehlivanoğlu, N., Uslu, H. & Kirbaşlar, S. I. (2010). Extractive separation of glutaric acid by
Aliquat 336 in different solvents. Journal of Chemical & Engineering Data, 55, 9, 2970-
2973, ISSN: 0021-9568
Pham, T. P. T., Cho, C.-W. & Yun, Y.-S. (2010). Environmental fate and toxicity of ionic
liquids: a review. Water Research, 44, 2, 352-372, ISSN: 0043-1354
Plechkova, N. V. & Seddon, K. R. (2007) Ionic liquids: “Designer” solvents for green
chemistry, In Methods and Reagents for Green Chemistry, Perosa, A., Zecchini, F.
(Eds.), 105–130, John Wiley Sons, ISBN: 978-0-471-75400-8, NewYork
Rahman, M., Shoff, H. W. & Brazel, C. S. (2005). Ionic liquids as alternative plasticizers for
poly(vinyl chloride): flexibility and stability in thermal, leaching, and UV
environments. In Ionic Liquids in Polymer Systems, Brazel, C. S. & Rogers, R. D.
(Eds.), 103–118, American Chemical Society, ISBN: 9780841239364
Ramnial, T., Ino, D. D. & Clyburne, A. C. (2005). Phosphonium ionic liquids as reaction
media for strong bases. Chemical Communications, 3, 325-327, ISSN: 1359-7345
Ramnial, T., Taylor, S. A., Bender, M. L., Gorodetsky, B., Lee, P. T. K., Dickie, D. A.,
McCollum, B. M., Pye, C. C., Walsby, C. J. & Clyburne, J. A. C. (2008). Carbon-
centered strong bases in phosphonium ionic liquids. Journal of Organic Chemistry,
73, 3, 801-812, ISSN: 0022-3263
Regel-Rosocka, M. (2009). Extractive removal of zinc(II) from chloride liquors with
phosphonium ionic liquids/toluene mixtures as novel extractants. Separation and
Purification Technology, 66, 1, 19-24, ISSN: 1383-5866
Rickelton, W. A. & Robertson, A. J. (1982). US Patent 4 353 883
Rickelton, W. A., Flett, D. S. & West, D. W. (1984). Cobalt-nickel separation by solvent
extraction with bis(2,4,4 trimethylpentyl)phosphinic acid. Solvent Extraction and Ion
Exchange, 2, 6, 815-838, ISSN: 0736-6299
Robertson, A. J. (Cytec Industries) (2001). Phosphonium salts. WO 01/87900
Robertson, A. J. (1983). Process for the preparation of highly purified, dialkyl phosphinic
acids. US 4 374 780, WO/2006/047545A2
Robertson, A. L. & Seddon, K. R. (Cytec Industries) (2002). Phosphonium phosphinate
compounds and their preparation, WO 02/079212 A1
Rogers, R. D., Seddon, K. R. & Volkov, S. (Eds.) (2002). Green industrial applications of ionic
liquids. Kluwer Academic Publishers, ISBN: 1-4020-1136-9, Netherlands
Rosatella, A. A., Branco, L. C. & Afonso, C. A. M. (2009). Studies on dissolution of
carbohydrates in ionic liquids and extraction from aqueous phase. Green Chemistry,
11, 9, 1406-1413, ISSN: 1463-9262
Rup, S., Zimmermann, F., Meux, E., Schneider, M., Sindt, M. & Oget, N. (2009). The
ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium
tetroxide catalysis: Influence of the mixture of solvents. Ultrasonics Sonochemistry,
16, 2, 266-272, ISSN: 1350-4177

www.intechopen.com
678 Ionic Liquids: Theory, Properties, New Approaches

Seddon, K. R., Stark, A. & Torres, M.-J. (2000). Influence of chloride, water, and organic
solvents on the physical properties of ionic liquids. Pure and Applied Chemistry, 72,
12, 2275-2287, ISSN: 0033-4545
Seddon, K. R., Carmichael, A. & Earle, M. J. (2001). Process for preparing ambient
temperature ionic liquids, WO 01/40146 A1
Seeley, F. G. & Crouse, D. J. (1966). Extraction of metals from chloride solutions with amines.
Journal of Chemical & Engineering Data, 11, 3, 424-429, ISSN: 0021-9568
Selva, M., Tundo, P. & Perosa, A. (1998). Hydrodehalogenation of halogenated aryl ketones
under multiphase conditions 5. Chemoselectivity toward aryl alcohols over a Pt/C
catalyst. Journal of Organic Chemistry, 63, 10, 3266-3271, ISSN: 0022-3263
Srncik, M., Kogelnig, D., Stojanovic, A., Körner, W., Krachler, R. & Wallner, G. (2009).
Uranium extraction from aqueous solutions by ionic liquids. Applied Radiation and
Isotopes, 67, 12, 2146–2149, ISSN: 0969-8043
Stark, A., Ajam, M., Green, M., Raubenheimer, H. G., Ranwell, A. & Ondruschka, B. (2006).
Metathesis of 1-octene in ionic liquids and other solvents: effects of substrate
solubility, solvent polarity and impurities. Advanced Synthesis & Catalysis, 348, 14,
1934-1941, ISSN: 1615-4150
Starks, C. M. (1971). Phase-transfer catalysis I. Heterogeneous reactions involving anion
transfer by quaternary ammonium and phosphonium salts. Journal of the American
Chemical Society, 93, 1, 195-199, ISSN: 0002-7863
Stojanovic, A., Lämmerhofer, M., Kogelnig, D., Schiesel, S., Sturm, M., Galanski, M.,
Krachler, R., Keppler, B. K. & Lindner, W. (2008). Analysis of quaternary
ammonium and phosphonium ionic liquids by reversed-phase high-performance
liquid chromatography with charged aerosol detection and unified calibration.
Journal of Chromatography A, 1209, 1-2, 179–187, ISSN: 0021-9673
Stojanovic, A., Kogelnig, D., Fischer, L., Hann, S., Galanski, M., Grössl, M., Krachler, R. &
Keppler, B. K. (2010). Phosphonium and ammonium ionic liquids with aromatic
anions: Synthesis, properties, and platinum extraction. Australian Journal of
Chemistry, 63, 3, 511-524, ISSN: 0004-9425
Sun, X., Ji, Y., Chen, J. & Li., D. (2010a). An engineering - purpose preparation strategy for
ammonium -type ionic liquid with high purity. AIChE Journal, 56, 989-996, ISSN:
0001-1541
Sun, X., Ji, Y., Zhang, L., Chen, J. & Li, D. (2010b). Separation of cobalt and nickel using inner
synergistic extraction from bifunctional ionic liquid extractant (Bif-ILE). Journal of
Hazardous Materials, 181, 1-3, 447-452, ISSN: 0304-3894
Tariq, M., Forte, P. A. S., Costa Gomes, M. F., Canongia Lopes, J. N. & Rebelo, L. P. N.
(2009). Densities and refractive indices of imidazolium- and phosphonium-based
ionic liquids: Effect of temperature, alkyl chain length, and anion. Journal of
Chemical Thermodynamics, 41, 6, 790-798, ISSN: 0021-9614
Tseng, M.-C., Kan, H.-C. & Chu, Y.-H. (2007). Reactivity of trihexyl(tetradecyl)phosphonium
chloride, a room temperature phosphonium ionic liquid. Tetrahedron Letters, 48, 52,
9085-9089, ISSN: 0040-4039

www.intechopen.com
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering 679

Tundo, P., Perosa, A., Selva, M. & Zinovyev, S. S. (2001). A mild catalytic detoxification
method for PCDDs and PCDFs. Applied Catalysis B: Environmental, 32, L1-L7, ISSN:
0926-3373
Uddin, M. S., Hidajat, K., Lim, B.-G. & Ching, C.-B. (1990). Interfacial mass transfer in
extraction of amino acid by Aliquat 336 in organic phase. Journal of Chemical
Technology and Biotechnology, 48, 4, 415-426, ISSN: 0268-2575
Uslu, H. & Kirbaşlar, I. S. (2009). Investigation of phase equilibria of levulinic acid
distribution between aqueous phase to organic phase by Aliquat 336 in different
modifiers. Journal of Chemical Thermodynamics, 41, 9, 1042-1048, ISSN: 0021-9614
Van den Berg, C., Roelands, C. P. M., Bussmann, P., Goetheer, E. L. V., Verdoes, D. & van
der Wielen, L. A. M. (2009). Preparation and analysis of high capacity polysulfone
capsules. Reactive & Functional Polymers, 69, 10, 766-770, ISSN: 1381-5148
Villa, C., Mariani, E., Loupy, A., Grippo, C., Grossi, G. C. & Bargagna, A. (2003). Solvent-free
reactions as green chemistry procedures for the synthesis of cosmetic fatty esters.
Green Chemistry, 5, 5, 623-626, ISSN: 1463-9262
Wang, L., Paimin, R., Cattrall, R. W., Shen, W. & Kolev, S. D. (2000). The extraction of
cadmium(II) and copper(II) from hydrochloric acid solutions using an Aliquat
336/PVC membrane. Journal of Membrane Science, 176, 1, 105-111, ISSN: 0376-7388
Wasserscheid, P. & Welton, T. (2008). Ionic Liquids in Synthesis, second edition, Wiley-VCH,
ISBN 978-3-527-31239-9, Weinheim, Germany
Welton, T. (1999). Room-temperature ionic liquids. Solvents for synthesis and catalysis.
Chemical Reviews, 99, 8, 2071-2083, ISSN: 0009-2665
Wells, A. S. & Coombe, V. T. (2006). On the freshwater ecotoxicity and biodegradation
properties of some common ionic liquids. Organic Process Research & Development,
10, 4, 794-798, ISSN: 1083-6160
Weng, J., Wang, C., Li, H. & Wang, Y. (2006). Novel quaternary ammonium ionic liquids
and their use as dual solvent-catalysts in a hydrolytic reaction. Green Chemistry, 8, 1,
96-99, ISSN: 1463-9262
Werner S., Haumann, M. & Wasserscheid, P. (2010). Ionic liquids in chemical engineering,
Annual Review of Chemical and Biomolecular Engineering, 1, 203-230, ISSN: 1947-5438
Wolff, M. O., Alexander, K. M. & Belder, G. (2000). Uses of quaternary phosphonium
compounds in phase transfer catalysis. Chimica Oggi, 18, 1/2, 29-32, ISSN: 0392-
839X
Yadav, G. D. & Motirale, B. G. (2008). Ionic liquid as catalyst for solid-liquid phase transfer
catalyzed synthesis of p-nitrodiphenyl ether. Industrial & Engineering Chemistry
Research, 47, 23, 9081-9089, ISSN: 0888-5885
Yadav, G. D. & Tekale, S. P. (2010). Selective O-alkylation of 2-naphtol using phosphonium-
based ionic liquid as the phase transfer catalyst. Organic Process Research &
Development, 14, 3, 722-727, ISSN: 1083-6160
Yang, W. W., Luo, G. S. & Gong, X. C. (2005). Extraction and separation of metal ions by a
column packed with polystyrene microcapsules containing Aliquat 336. Separation
and Purification Technology, 43, 2, 175-182, ISSN: 1383-5866
Yao, C., Pitner, W. R. & Anderson, J. L. (2009). Ionic liquids containing the
tris(pentafluoroethyl)trifluorophosphate anion: a new class of highly selective and

www.intechopen.com
680 Ionic Liquids: Theory, Properties, New Approaches

ultra hydrophobic solvents for the extraction of polycyclic aromatic hydrocarbons

using single drop microextraction. Analytical Chemistry, 81, 12, 5054-5063, ISSN:
0003-2700
Yuan, X. L., Zhang, S. J. & Lu, X. M. (2007). Hydroxyl ammonium ionic liquids: synthesis,
properties, and solubility of SO2. Journal of Chemical & Engineering Data, 52, 2, 596–
599, ISSN: 0021-9568

www.intechopen.com
 Ionic Liquids: Theory, Properties, New Approaches
Edited by Prof. Alexander Kokorin

ISBN 978-953-307-349-1
Hard cover, 738 pages
Publisher InTech
Published online 28, February, 2011
Published in print edition February, 2011

Ionic Liquids (ILs) are one of the most interesting and rapidly developing areas of modern physical chemistry,
technologies and engineering. This book, consisting of 29 chapters gathered in 4 sections, reviews in detail
and compiles information about some important physical-chemical properties of ILs and new practical
approaches. This is the first book of a series of forthcoming publications on this field by this publisher. The first
volume covers some aspects of synthesis, isolation, production, modification, the analysis methods and
modeling to reveal the structures and properties of some room temperature ILs, as well as their new possible
applications. The book will be of help to chemists, physicists, biologists, technologists and other experts in a
variety of disciplines, both academic and industrial, as well as to students and PhD students. It may help to
promote the progress in ILs development also.

How to reference
In order to correctly reference this scholarly work, feel free to copy and paste the following:

Anja Stojanovic, Cornelia Morgenbesser, Daniel Kogelnig, Regina Krachler and Bernhard K. Keppler (2011).
Quaternary Ammonium and Phosphonium Ionic Liquids in Chemical and Environmental Engineering, Ionic
Liquids: Theory, Properties, New Approaches, Prof. Alexander Kokorin (Ed.), ISBN: 978-953-307-349-1,
InTech, Available from: http://www.intechopen.com/books/ionic-liquids-theory-properties-new-
approaches/quaternary-ammonium-and-phosphonium-ionic-liquids-in-chemical-and-environmental-
engineering

InTech Europe InTech China

University Campus STeP Ri Unit 405, Office Block, Hotel Equatorial Shanghai
Slavka Krautzeka 83/A No.65, Yan An Road (West), Shanghai, 200040, China
51000 Rijeka, Croatia
Phone: +385 (51) 770 447 Phone: +86-21-62489820
Fax: +385 (51) 686 166 Fax: +86-21-62489821
www.intechopen.com