IONIC LIQUID

ABSTRACT
This includes a brief introduction of ionic liquid,their charteristics reflecting their physical and chemical properties for instance molar conductivity,polarity, dilelectic constant ,temp variance etc. It also includes the electrochemistry of ionic liquid , their brief detection process. Major differences is also established between different ionic liquids with their applications.

INTRODUCTION
An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below some arbitrary temperature, such as 100 C (212 F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutralmolecules, ILs are largely made of ions and short-lived ion pairs. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses. ILs have many applications, such as powerful solvents and electrically conducting fluids

(electrolytes). Salts that are liquid at near-ambient temperature are important for electric batteryapplications, and have been used as sealants due to their very low vapor pressure. Any salt that melts without decomposing or vaporizing usually yields an IL. Sodium chloride(NaCl), for example, melts at 801 C (1,474 F) into a liquid that consists largely of sodium cations (Na+) and chloride anions (Cl). Conversely, when an IL is cooled, it often forms an ionic solidwhich may be either crystalline or glassy. The ionic bond is usually stronger than the Van der Waals forces between the molecules of ordinary liquids. For that reason, common salts tend to melt at higher temperatures than other solid molecules. Some salts are liquid at or below room temperature. Examples include pyridinium chloride, C5H6N+Clthat melts at 144.5 C (292.1 F); 1-ethyl-3-methylimidazolium dicyanamide, (C2H5)(CH3)C3H3N2+N(CN)2 , that melts at 21 C (6 F); and 1-butyl-3,5-dimethylpyridinium bromide which becomes a glass below 24 C (11 F).

Low-temperature IL can be compared to ionic solutions, liquids that contain both ions and neutral molecules, and in particular to the so-called deep eutectic solvents, mixtures of ionic and non-ionic solid substances which have much lower melting points than the pure compounds. Certain mixtures of nitrate salts can have melting points below 100 C

DISCUSSION
HISTORY
The discovery date of the "first" ionic liquid is disputed, along with the identity of its discoverer. Ethanolammonium nitrate (m.p. 5255 C) was reported in 1888 by S. Gabriel and J. Weiner. One of the earliest truly room temperature ionic liquids was ethylammonium nitrate (C2H5)NH3+NO3-) (m.p. 12 C), synthesized in 1914 by Paul Walden. In the 1970s and 1980s ionic liquids based on alkylsubstitutedimidazolium and pyridinium cations, with halide or trihalogenoaluminate anions, were initially developed for use as electrolytes in battery applications.

CHARACTERISTICS
Ionic liquids are often moderate to poor conductors of electricity, non-ionizing (e.g. non-polar), highly viscous and frequently exhibit low vapor pressure. Their other properties are diverse: many have low combustibility, excellent thermal stability, wide liquid regions, and favorable solvating properties for a range of polar and non-polar compounds. Many classes of chemical reactions, such as Diels-Alder reactions and Friedel-Crafts reactions, can be performed using ionic liquids as solvents. Recent work has shown that ionic liquids can serve as solvents for biocatalysis. The miscibility of ionic liquids with water or organic solvents varies with side chain lengths on the cation and with choice of anion. They can be functionalized to act as acids, bases or ligands, and have been used as precursor salts in the preparation of stable carbenes. Because of their distinctive properties, ionic liquids are attracting increasing attention in many fields, including organic chemistry,electrochemistry, catalysis, physical instance magnetic ionic liquid. chemistry, and engineering; see for

Commonly used cations for ionic liquids Despite their extremely low vapor pressures, some ionic liquids can be distilled under vacuum conditions at temperatures near 300 C.In the original work by Martyn Earle, et al., the authors wrongly concluded that the vapor was made up of individual, separated ions.but was later proven that the vapors formed consisted of ion-pair.
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Some ionic liquids (such as 1-butyl-3-

methylimidazolium nitrate) generate flammable gases on thermal decomposition. Thermal stability and melting point depend on the liquid's components. Thermal stability of various RTILs (Room Temperature Ionic Liquid) are available. The thermal stability of a task-specific ionic liquid, protonated betaine bis(trifluoromethanesulfonyl)imide is of about 534 K (502 F) and N-Butyl-NMethyl pyrrolidinium bis(trifluoromethanesulfonyl)imide was thermally stable up to 640 K.The upper limits of thermal stability of ionic liquids reported in the literature are usually based upon fast (about 10 K/min) TGA scans, and they do not imply long-term (several hours) thermal stability of ionic liquids, which is limited to less than 500 K for most ionic liquids.] The solubility of different species in imidazolium ionic liquids depends mainly on polarity and hydrogen bonding ability. Saturated aliphatic compounds are generally only sparingly soluble in ionic liquids, whereas olefins show somewhat greater solubility, and aldehydes can be completely miscible. This can be exploited in biphasic catalysis, such as hydrogenation and hydrocarbonylation processes, allowing for relatively easy separation of products and/or unreacted substrate(s). Gas solubility follows the same trend, with carbon dioxide gas showing exceptional solubility in many ionic liquids. Carbon monoxide is less soluble in ionic liquids than in many popular organic solvents, and hydrogen is only slightly soluble (similar to the solubility in water) and may vary relatively little between the more commonly used ionic liquids. Different analytical techniques have yielded somewhat different absolute solubility values. The properties of ionic liquid are summarized in given table (table 1)

A salt Freezing point

Cation and or anion quite large Preferably below 100

Liquidus range Thermal stability Viscosity Dielectric constant Polarity Specific conductivity Molar conductivity Electrochemical window Solvent and/or catalyst Vapor pressure

Often > 200 Usually high Normally < 100 cP, workable Implied < 3 Moderate Usually < 10 mScm-1, Good < 10 Scm2mol-1 > 2V, even 4.5 V, except for Brnsted acidic systems Excellent for many organic reactions Usually negligible

Liquids Comparisons
How do these ionic liquids compare with other liquids, especially those which conduct electricity? Table below represent this (table 2) Compound Ionic Liquid NaCl LiCl NaNO3 Na2SiO3 AlCl3(63%) NaCl LiCl-KCl [(CH3)3S][ HBr2] emimCl(60%)-AlCl3 emim Al2Cl7 Temp. (C) 900 780 450 1750 175 450 25 25 25 Molarity (Mol L-1) 25.3 13 21.4 18 5.8 29.7 7.3 5.3 3.4 Spec Cond (Scm-1) 3.88 7.59 0.72 4 0.24 1.57 0.034 0.0065 0.015 Molar Cond (Scm2 mol-1) 154 217 34 270 41 53 4.7 1.2 4.4 3.85 2.44 20.5 47 14 6.9 Visc. (cP) 1.05 Ref

2 2 2 2 7 7 8 8 8

bmim CF3CO2 bupy BF4 emim[(CF3SO2)2N] H2O 0.1 M aq. KCl Na H2SO4 CH3COOH HF

20 25 25 25 25 100 25 25 0

5.1 5.5 3.7 5.3a 0.1b 40.4 0.049b 17.5 a 50.1a

0.0032 0.0019 0.0057 4 x 10-8 0.013 1.04 x 10 0.0104 8 x 10 1 x 10-5

0.6 0.3 1.5 7x10-7 129 2.6x106 212 4.6x10-7 2x10-5

73 103 31 0.895 0.9 1.058 24.55 1.056 0.256

8 8 8 2 2 2 9 10 9

a = total molarity b = ionic molarity emim = 1-ethyl-3-methyl-1H-imidazolium bmim = 1-butyl-3-methyl-1H-imidazolium bupy = 1-butylpyridinium One property that emphasized recently is the molarity of the liquid6 (a straightforward quantity except for mixed systems such as a basic chloroaluminate containing both Cl-and AlCl4- in significant amounts).The molarity is important regarding kinetic measurements, including conductivities.Table II indicates a range of molarities of many liquids from 1 o 60, with water at 55, liquid alkali halides up to 35(LiCl) and most organic salts less than 10. Specific conductivities span a far greater range from the metal sodium through molten inorganic salts in the Scm-1region to organic salts (the modern ionic liquids) and aqueous solutions in the mScm-1 region and finally to the near non-conducting but ionizing acetic acid and water at Scm-1Combining these data into .molar conductances is illuminating. We see comparable values for simple inorganic salts alone and in aqueous solutions* but much smaller values for the low temperature semi-organic and organic systems. Thus these modern ionic liquids must consistof IONS AND ION PAIRS, (undissociated molecules), while liquid alkali halides are purely IONIC and aqueous electrolytes behave as a mixture of hydrated ions and the molecular solvent water. Hmim+ and py+Anions such as NO3 .- ,AlCl4- and PF6- derive from Lewis acid base reactions:O2- + N2O5--Cl- + AlCl3-t AlCl4-F- + PF5-t PF6-ions to add further Lewis acids to form acidic ions, e.g., Al2Cl7-, Sb2F11-, HBr2-.As a result we can obtain Lewis basic, neutral or acidic ionic liquids, exemplified by the well-researched haloaluminates. In addition we can make protic acidic liquids which are simultaneously of any Lewis aspect.12How is proton chemistry in ionic liquids related to proton chemistry in liquids often occur as anions, e.g., HCl2-, HBr2-, H2Br3-, rather than cations. Second, protons bonded to basessuch as pyridine and lmethylimidazole are not labile.13 Do bases behave in line with their pkb s in water? No. Bases in ionic liquids appear to act in accordance with their gas phase proton affinities (l-

methylimidazole > pyridine > ammonia).14 The complicating factor of course is solvation in water. One can, however, obtain Hammett acidity data for some systems which make fair chemical sense.

What happens when water is added to an ionic liquid or not completely removed at some stage in its
preparation? 1. Some anions such as AlCl4-and HCl2- are irreversibly decomposed. 2. Water may bind strongly to one of the ions. 3. Water may dissolve the liquid until it forms a saturated salt solution; unlike the case of dissolving a solid salt, the other phase will be liquid and it may or may not contain water. 4. At high temperatures, species such as Li(H2O) +Cl-may decompose to LiOH and HCl.

Electrochemistry of Ionic Liquids

The General SituationOnce we have established from conductivity measurements that a liquid is ionic (not ionic/molecular), its temperature and complexity should not pose special problems for using it as a solvent for electrochemistry. With inorganic cations, the solubility of a metal in its salt may arise while the reduction of organic cations is complex and irreversible. Following chemical reactions such as attack of an electrode reaction product on the opposite ion in the system can also occur (F2vs. bmim+17 ,O2-vs. NO3- .Electrode processes of ionic solvent includes Cation Reduction, Anion Reduction, Anion Oxidation , Proton Reaction.

Detection of Ionic Liquid

The following (Scheme 1) is a sequence of steps prompted by finding two 19th century pieces of work: (a) Gardner s observation of maximum boiling point compositions for mixtures of several bases with acetic acid (he incorrectly called these specific mixtures compounds not azeotropes); and (b) Zawidzki s vapor pressure studies1 of pyridine mixed with formic, acetic and propionic acids Scheme 1. Detecting an ionic liquid. a) For an acid-base system HA + B: Clue #1 Vapor pressures of some mixtures show large negative deviation from Raoult s law: compound forms Clue #2/H NMR spectra show downfield shift of HA s proton with B addition: BHA is ionized to BH+A Clue #3 Some mixtures show s values in the mScm-1range, far greater than for the components: BH+A dissociates overall chemistry B + HA } BH+A-} BH+ + A is then governed by the ionization and

dissociation constants and with the ionic liquid containing the ions BH+ and A- and the ion-pair BH+A-.20-22 In practice, one may also have to include the self-ionization of HA and the formation of hydrogenates HnAn+1-. (b) For the salt MX or BRA where R = alkyl: Clue #1 Very low vapor pressures: stable compound in liquid Clue #2 NMR data less dramatic: may suggest BR+A Clue #3 s values at least in the mScm-1 range: MX or BR+A- dissociationFor the acid-base systems the vapor may consist of the ionic compound or the original components,23whereas the breakdown of BR+A- (e.g., emimCl) into B and RA is probably irreversible.24,25The behavior of the vapor should correlate with the gas phase proton affinities.

APPLICATION
ILS find a variety of industrial applications. A few industrial applications are described below; more detailed information can be found in a recent review article.

Dispersants : Gas handling:

ILs can act as dispersing agents in paints to enhance finish, appearance and drying

properties. ILs are used for dispersing nanomaterials at IOLITEC. ILs have several properties that make them useful in gas storage and handling applications, including low vapor pressure, stability at high temperatures, and solvation for a wide variety of compounds and gases. They also have weakly coordinating anions and cations which are able to stabilize polar transition states. Many ionic liquids can be reused with minimal loss of activity. IL 1-butyl-3-methylimidazolium chloride has been used for separating hydrogen from ammonia borane.

Gas treatment: ION

sweetening.

Engineering is commercializing ILs and amines for CO2 capture and natural gas

Batteries:

Researchers have identified ILs that can replace water as the electrolyte in metal-air

batteries. ILs have great appeal because they evaporate at much lower rates than water, increasing battery life by drying slower. Further, ILs have an electrochemical window of up to six volts.(versus 1.23 for water) supporting more energy-dense metals. Energy densities from 900-1600 watt-hours per kilogram appear possible. A Metal-air battery draws oxygen through a porous ambient "air" electrode (-cathode) and produces water, hydrogen peroxide, or hydroxide anions depending on the nature oxygen reduction catalyst and electrolyte. These compounds store the electrons released by the oxidation of the anode.

Chemical industry, Cellulose processing, Nuclear fuel reprocessing ,Solar thermal energy ,Food and bioproducts , High Purity Organometallics.
AND IN MANY OTHER FIELDS LIKE

CONCLUSION
An ionic liquid is characterized by a specific conductivity in the mScm-1 range as a minimum, together with a molar conductivity probably exceeding 0.1 Scm2 mol-1.In addition, the liquid should only containions with lesser numbers of ion pairs or parent molecules. Ionic liquids tend to have lowdielectric constants, which means they are not ionizing solvents. One can assign an ionicity to an ionic liquid in terms of its conductivity and, presumably one might attempt to describe any liquid in this manner but ignoring the chemical properties of excess solvent molecules could lead to significant errors.Thus in answer to the opening question, What is an ionic liquid? I prefer the answer, Just a liquid salt consisting of ions and ion pairs.

REFRENCES
* www.wikipedia.com * J. O M Bockris and A. K. N. Reddy, Modern Electrochemistry, Plenum, New York (1970) * The Structure and Properties of Ionic Melt Faraday Soc., 32, University Press, Aberdeen (1962) * www.electrochem.org