International Journal of Basic Sciences and Applied Computing (IJBSAC)

ISSN: 2394-367X, Volume-1 Issue-1, August 2014

Ionic Liquids-Designer Solvents for Green

Chemistry
Sadhana Vishwakarma

Abstract - Ionic liquids, as green solvents have been studied widely Many solvents used in large volumes for many decades have
now a days due to their appealing properties such as negligible been found to create serious toxic or otherwise hazardous
vapour pressure, large liquid range, high thermal stability, high properties. Halogenated solvents such as carbon tetrachloride,
ionic conductivity, large electrochemical window, and ability to
perchloroethylene, and chloroform, for example, have been
solvate compounds of widely varying polarity. Utilizing ionic
liquids is one of the goals of green chemistry because they create a implicated as probable and/or suspect carcinogens, while
cleaner and more sustainable chemistry and are receiving other classes of solvents have demonstrated
increasing interest as environmental friendly solvents for many neurotoxicological effects. The search for an unconventional
synthetic and catalytic processes. Ionic liquids have been solvent is an important step in making an analysis and
investigated for a wide range of synthetic applications, they have separation process “greener” and environmentally friendlier.
fascinated considerable interest for used as non-volatile solvent It appears that alternative solvents like ionic liquids (ILs) and
based electrolytes in the field of organic synthesis, catalysis, supercritical fluids have one extra aspect which makes them
electrochemistry, solar cells, fuel cells, etc., as they possess many
even more attractive for researchers—tunability. The ability
benefits than volatile organic solvents.
to fine-tune the properties of the solvent medium will allow
Index Terms— Green chemistry, applications, classification, this to be chosen to replace specific solvents in a variety of
ionic liquids, properties. different processes or generate new methods for processing
(analyzing) samples. Ionic liquids supposed as novel
I. INTRODUCTION chemical agents and widely regarded as a greener substitute to
The Need for Green Solvents many commonly used solvents because they are designable,
Transferring waste into useful products is one way to improve recyclable and non-volatile.
“greenness.” Another move toward “source prevention is the
final goal in the field of green chemistry. If we want to avoid II. WHAT ARE IONIC LIQUIDS?
the toxic effects of a substance, don’t generate it in the first The terms room-temperature ionic liquid (RTIL), nonaqueous
place” (Wilkinson, 1997). -The utilization of solvents in the ionic liquid, molten salt, liquid organic salt, and fused salt
chemical industry and in the chemical-related industries is have all been used to explain salts in the liquid phase (Welton
very common. Beyond “chemical industries,” solvent use has T.1999). Ionic liquids are composed exclusively of anions
become an essential part of life in the twenty-first century. In and cations. They are molecular solvents composed of neutral
1991, the manufacturing of the 25 most commonly used species such as benzene, methanol, chloroform, water etc.
solvents was more than 26 million tons per year. Five of the Usual molten salts show a high melting point (i.e., 801 ◦C for
top 10 chemicals disposed of were solvents like methanol, sodium chloride and 614 ◦C for lithium chloride), which
toluene, xylene, methyl ethyl ketone, and dichloromethane. greatly confine their use as solvents in most applications.
The total amount of these chemicals released or disposed of RTILs, however, continue to be liquids at or below room
was over 687 million pounds, which accounts for 27% of the temperature. The adopted upper temperature limit for the
total quantity of TRI-listed chemicals released and disposed classification "ionic liquid" is 100 °C (though some solidify to
of in that year (Sullivan, 1997). Because solvents are essential glasses on cooling) and higher melting ion systems are
in such high volumes that, hazards associated with them and normally referred to as molten salts( Visser et.al 2002)
safety issues associated with their use have always been a A. Why are they Chemically Interesting?
concern in the development and selection of solvents. Some of These are liquids with broad temperate range and slight
the initial and most noticeable hazards, that if solvents -were vapour pressure. For example1-butyl-3-methylimidazolium
found to possess would cause them to be selected against, hexafluorophosphate shows steadiness in air upto 300oC.
include properties such as high flammability or explosivity. Ionic liquids exhibit excellent solvent properties and can often
With the greater understanding of the health and aid and influence chemical reactions without being altered in
environmental effects that could be caused by other hazardous the process (Welton, 1999). An ionic liquid is a salt in which
properties that solvents may possess or by their use in such the ions are weakly coordinated, which results in these
large volumes, alternative solvents are being carefully solvents being liquid below 100°C, or even at room
scrutinized for all hazardous properties, and new solvent temperature (room temperature ionic liquids, RTIL's). At
systems are being developed to be more environmentally least one ion has a delocalized charge and one component is
benign. organic, which prevents the formation of a stable crystal
lattice (Wasserscheid ,2000). Due to the large amount of
possible combinations of cation and anion, they are
Manuscript Received on August 2014.
vulnerable to numerous permutations that allow the various
Prof. Sadhana Vishwakarma, Technocrats Institute of Technology,
Bhopal, India. physical and chemical properties to be adjusted almost at will

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 Ionic Liquids-Designer Solvents for Green Chemistry

(Anon, 2001).
B. Classification of Ionic Liquids:
A simple ionic liquid consists of one cation and one anion.
The anions are generally small and the cations bulky with
alkyl chains. Some usually used anions for simple ionic liquid
systems are Cl, Br, BF4, CF3SO3 (OTf), N(SO2CF3)2
(NTf2) etc. There are a few dissimilar commonly used
cations for ionic liquids, the commonly studied ones are the
1-alkyl-3-methyl-imidazolium cations. Other cations are
phosphorus or nitrogen containing organic ions with attached
alkyl chains of varied length.

C. Physicochemical Properties of ILS

Study and synthesis of ionic liquids is still very latest, and they
reveal a wide range of properties. The ionic liquids (also
called as Room temperature ionic liquids) stay liquid in a
temperature range that is broader than that of other liquids.
Most of 1-alkyl-3-methyl-imidazolium ionic liquids have a
glass transition temperature between -10oC and -60oC and
are chemically stable in the temperature rang of
250oC-400oC depending on the alkyl chain length and the
selection of anion. Ionic liquids normally form glasses when
below their melting point and also demonstrate a strong
tendency for supercooling ( Bonhote et.al 1996). The high
The name of an ionic liquid first states the cation followed by
temperature acceptance and insignificant vapor pressure
the anion. For the most commonly studied systems
makes ionic liquids ideal for reactions at high temperature.
(imidazolium based cations) the cations are named according
The melting point of ionic liquids reduces with rise in alkyl
to the alkyl chains lengths followed by imidazolium. A
chain length and increases with increase in the degree of
1-butyl-3-methyl-imidazolium cation are sometimes
symmetry. The heat capacity of some commonly used
abbreviated as C4C1Im, BMIm, BMIM, bmim or ByMeIm.
imidazolium based iionic lidquids were reported in 2003
The anions are generelly named in accordance to general
(Holbrey et.al 2003). Negligible vapor pressure of the
principles, eg. Ac meaning Acetate. More than 600 ionic
majority of the ionic liquids is due to the tough Columbic
liquid systems can, in principle, be generated from around 10
forces between the anions and cations of the liquid. Ionic
simple anions such as (BF4)− and (PF6)− and the
liquids are more viscous then organic solvents sometimes by
1-alkyl-3-methylimidazolium cation substituted with various
several times. The extensive variation of the physicochemical
properties of ionic liquids and the simplicity with which the
design of the ionic liquid can be changed gave ionic liquids
the name “designer solvents” in the latter part of the 1990s.
Usually ionic liquids are polar solvents due to presence of
cation and anion but it can dissolve both polar and nonpolar
solutes due to its polarity i.e. salvation capability. In ionic
liquids salvation takes place due to ion-ion interactions, van
der Waal’s forces, dipole interaction as well as pi-pi
interactions. The solubility of ionic liquids in water is of great
consideration. The extent of solubility in water depends
mostly on the degree of coordination feasible with the ions.
Basic ions (NO3)- can strongly coordinate with water, while
acidic ions are non-coordinating and neutral ions (BF4)- and
(NTf2)- are weakly coordinated with water. The length of
alkyl chains on the cation also affects the miscibility of water
alkyl groups in the 2-, 4-, or 5-position, or N-alkylpridinium in an ionic liquid. A larger chains result in a more
substituted in the 3- or 4-position. When heteropolyanions hydrophobic ionic liquid (Wassercheid, 2000).
and tetralkylammonium and tetraalkylphosphonium cations
D. Preparation of Ionic Liquids
are added to the list, a grand total of more than a quarter of a
million ionic liquid systems is possible. With this enormous Ionic liquids can be made by three methods namely
variety, it is usually feasible to tailor the solvents to specific quatermerization, metathesis of halide, and direct
chemical reactions. Ionic liquids have a range of physical combination of halide salt with metal halide.
chemical properties that can be tuned with an accuracy that is
hard to see for a given reaction.

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 International Journal of Basic Sciences and Applied Computing (IJBSAC)
ISSN: 2394-367X, Volume-1 Issue-1, August 2014

Metathesis of Halide:
A great many ionic liquids are made by a metathesis reaction
from a halike or similar salt of the desired cation. The
meththesis reaction can be divided into two categories on the
basis of water solubilituy of the target ionic liquid :
metathesis via metal salts and Methathesis via Ag salt ( Wikes
et.al 1990).
R+X + M+A- R+A- + M+X+

Quaternization Reaction:
Most quaternization reactions involving an annular nitrogen
atom and alkylating agent proceed by means of SN2 reaction
in which inversion of configuration of an achiral reagent takes
place. The majority of such reactions give products reflecting
kinetic control. Products usually are formed irreversibly.
Alkyl halides are extensively used as alkylating agents in a
quaternization reactions. In this reaction the amine and the
E. Applications of Ionic Liquids:
preferred alkyl halide are mixed and the reaction mixture is
heated in an inert N or Argon atmosphere (Bonhote et.a. 1995 ILs find a great variety of industrial applications. A few
and Chauvin 1995).The quaternization can also be carried out industrial applications are given below:
under microwave situation (Namboodiri et.al.2002) Chemical Processes : Ionic liquids are found to be promising
solvents in many of the organic reaction such as Diels-Alder,
Comparison of Organic Solvents with Ionic Liquids* Bails-Hillman, Heck Reaction, esterification, isomerization
Property Organic Solvnets Ionic Liquid reactions and many coupling reaction( Kumar A., 2005 and
Number of >1000 >1,000,000 Fischer T., 1999)
solvents Electrochemical Devices : Excellent reviews are published
Applicability Single function Multi function indicating the applications of ionic liquids to electrochemical
Catalyticability Rare Common and devices such as super capacitors, lithium ion batteries,
tuneable polymer-electrolyte fuel cells and dye-sensitized solar cells.
Vapour Obeys the Negligible In an electrochemical apparatus, an ionic liquid acts as
pressure Clausius-Clapreyron vapour pressure electrolyte ( Lu W. et.al. 2002 and Silvester D., 2006).
Equation under normal Extraction Technology : Solvent extraction is used in nuclear
conditions reprocessing, ore processing, the production of fine organic
Chirality Rare Common and compounds, processing of perfumes and other industries. The
Tuneable application of ionic liquids to separate toxic metal ions and
Flammability Usually flammable Usually organic molecules has been investigated. Presently, ionic
nonflammable liquids have been used as extraction solvents for the
Polarity Conventional Questionable extraction of metal ions by crown ethers. Hence, ionic liquids
polarity have got much more attention in extraction processes (Ahou
Tuneability Limited range of Virtually D.et.al.2003 and Dai S. 1997).
solvent available unlimited range Pharmaceuticals: Recognizing that approximately 50% of
i.e. designer commercial pharmaceuticals are organic salts, ionic liquid
solvents forms of a number of pharmaceuticals have been investigated.
Cost Normally cheap 2-100 times Combining a pharmaceutically active cation with a
costly than pharmaceutically active anion leads to a Dual Active ionic
organic solvents liquid in which the actions of two drugs are combined (
Recyclability Green imperative Economic Stoimenovski J et.al 2010 and Frank P et.al 2013).
imperative Gas Handling: ILs have several properties that make them
Viscosity, cP 0.2-100 22-40,000 useful in gas storage and handling applications, including low
Desnsity, 0.6-1.7 0.8-3.3 vapor pressure, steadiness at high temperatures, and solvation
g/cm3 for a wide variety of compounds and gases. They also have
Refractive 1.3-1.6 1.5-2.2 weakly coordinating anions and cations which are able to
index stabilize polar transition states. Many ionic liquids can be
*Plechkova, 2008 reused with minimal loss of activity.

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 Ionic Liquids-Designer Solvents for Green Chemistry

Solar Thermal Energy: ILs have potential as a heat transfer [11] A. O'Sullivan, "Cellulose: the structure slowly unravels." Cellulose,
1997, vol.4(3),pp. 173-207.
and storage medium in solar thermal energy systems.
[12] P Wassercheid and W. Keim. “Ionic Liquids-new solutions for
Concentrating solar thermal facilities such as parabolic transition metal catalysis” , Angewandte Chemie-International
troughs and solar power towers center the sun's energy onto a Edition, 2000, vol.39, pp. 3772-378.
receiver which can generate temperatures of around 600 °C [13] P.Bonhote, A.P.Dias, N.Papageorgiou, K. Kalyanasundaram and M.
(1,112°F). This heat can then produce electricity in a steam or Gratzel. “Hydrophobic, high conductive ambient-temperatrure molten
salts”, Inorganic Chemistry, 1996, vol.35, pp.1168-1178.
other cycle [14] N.V. Plechkova, K.R. Seddon Chem Soc.Rev 2008, vol.37, pp.
Waste Recycling: ILs can help the recycling of synthetic 123-150.
goods, plastics and metals. They suggest the specificity [15] A.E. Visser, R.P. Swatloski, W.M. Reichert, R. Mayton, S.Sheff,
required to separate similar compounds from each other, such A.Wierzbicki, J.H. Davis, R.D. Rogers. "Task-specific ionic liquids
incorporating novel cations for the coordination and extraction of hg2+
as separating polymers in plastic waste streams. This has been and cd2+: synthesis, characterization, and extraction studies".
achieved using lower temperature extraction processes than Environ.Sci.Technol, 2002, vol. 36(11), pp. 2523-2529.
current approaches[50] and could help avoid incinerating [16] T Welton, "Room-temperature ionic liquids. solvents for synthesis and
plastics or dumping them in landfill. catalysis", Chem.Rev., 1999, vol.99(8), pp. 2071-2084.
[17] J.S. Wikes, M.J. Zaworotko, J.Chem.Soc. Chem.Commun, 1990,
Batteries: Researchers have recognized ILs that can substitute pp.965.
water as the electrolyte in metal-air batteries. ILs have great [18] S. L. Wilkinson, Chemical & Engineering News, 1997, vol.75,
potential because they evaporate at much lower rates than pp.35–43.
water, increasing battery life by drying slower. Further, ILs [19] D. Zhou, G. M. Spinks, G. G. Wallace, C. Tiyapiboonchaiya, D. R.
MacFarlane, M.Forsyth & J. Sun, Electrochim Acta, 2003, vol. 48,
have an electrochemical window of up to six volts [51](versus pp.2355-2370.
1.23 for water) supporting more energy-dense metals. Energy
densities from 900-1600 watt-hours per kilogram appear Dr. Sadhana Vishwakarma, is born in Nagpur on
possible. 14thAugust 1967. She completed her under graduation
from Shri Shivaji Education Society, Nagpur, India, in
1988 and stood third in order of merit and received Gold
III. CONCLUSION
medal in Zoology. She completed her post graduation in
Ionic liquids believed as novel chemical agents and widely organic chemistry in 1990 from Science College, Nagpur,
regarded as a greener alternative to many frequently used India and stood first in order of merit and received gold medal in Organic
chemistry. In 1991 she has completed her degree in Education from Nagpur
solvents because they are designable, recyclable and
university, India and diploma in pharmacy in 2005 from Karnataka Board,
nonvolatile. Based on it, ionic liquids have been studied for a Karnataka, India. She has completed her MSCIT certificate course in 2005.
wide range of synthetic applications, they have attracted She acquire Ph.D. from Nagpur University in 1996 and topic of the thesis
considerable interest for used as non-volatile solvent based was “ Recovery of value added chemicals from fermentation broth”. She has
2 years research experience as junior project fellow under DBT sponsored
electrolytes in the areas of organic synthesis, catalysis,
project “ Production of 2,3-butanediol from water hyacinth and 3years
electrochemistry, solar cells, fuel cells, etc., as they possess experience as senior project fellow under the DBT sponsored project“
many benefits than volatile organic solvents. Several studies Production of Hydrogen and chemicals from waste” in National
indicate the successful synthesis of ionic liquids using simple Environmental Engineering Research Institute (NEERI), Nagpur, India. She
worked as Head of the Department of Medical Laboratory Technology in
chemical reactions for large extent processes.
Gramin Polytechnique, Vishnupuri, Nanded, India successfully for 9 years.
Then she worked as Assistant Professor of chemistry in All Saints’ college,
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