Ionic Liquid

By Nila T Berghuis
Week: 14
What are Ionic Liquids
Discovery and History
Paul Walden
• * The description of a low melting point salt - 1914
• Ethyl ammonium nitrate
• * The first room temperature ionic liquid - 1951
• N-ethylpyridinium bromide- aluminium chloride
melt
• * The most stable and conductive salts - 1982
• 1,3-dialkylimidazolium salts
• * The hydrophobic ionic liquids -
1992
• 1-ethyl-3-methylimidazolium tetrafluoroborate
Common Definition

• Ionic Liquids (ILs) is the generic

term for a class of materials,
consisting entirely of ions and
being liquid below 100°C.

• If they are liquid at room

temperature, we call them room
temperature ionic liquids (RTILs).
Why are ionic liquids is “liquids” ?
 Ionic Liquids - Introduction

NaCl (mp 801°C) BMIm PF6 (mp -79°C)

• Ionic liquids are salts, with melting points below ambient temperature
• They are composed solely of anions and cations – no water is present
• Their regular, ordered structure gives them very different properties to
conventional liquids
• Ionic liquids based on imidazole have been well studied as novel solvents
 “First Generation” Ionic Liquids - Disadvantages

F
F F
P-
N
+ N F F
F

• Expensive in comparison with molecular solvents.

• Very few commercially available.
• Viscous
• Poorly biodegradable and potentially toxic.
The methylimidazolium and pyridinium ions have proven to be good starting points for the
development of ionic liquids:
Properties, such as
melting point, viscosity,
and solubility of starting
materials and other
solvents, are determined
by the substituents on
the organic component
and by the counterion.
 “Second Generation” Ionic Liquids

CH3 O

N -O
HO H+ CH3 CH3

• Bioniqs has developed new types of simple ionic liquids, based on

ammonium salts.
• These retain the advantages of ionic liquids, but also offer:
• - reduced viscosity.
• - low cost.
• - straightforward preparation from sustainable precursors.
• - minimal toxicity and environmental impact.
• - recyclability and biodegradability.
 Ionic Liquids - Properties

• Extremely good solvents for many compounds – organic, inorganic, mineral,

polymeric and biological
• Non-volatile – do not evaporate
• Non-flammable
• Stabilize sensitive compounds
• Many possible combinations of ions – can design the solvent for a
particular application
Melting points
Ionic liquids:
Polarity (adjustable)
Very low vapor pressure
Liquid ranges (> 300 °C)
Solubility of gases & a wide
range of compounds
Immiscibility with solvents
Hydrophilicity/lipophilicity
(adjustable)
Acidity (adjustable)
 Charge distribution for
[C4mim][PF6]. (4-1-PF6)
Red corresponds to regions
of high relative negative
charge, and blue to high
relative positive charge.

New ionic liquid made up

of a cobalt-carbonyl anion
and imidazolium cation.
The liquid is catalytically
active in its own right.
Ionic liquids can form structures in their own right such
as a stable smectic liquid crystal eg. [C14mim][PF6].

Ionic liquids made of dialkylimidazolium cations

and appropriate anions are useful alternative
media of special properties to be employed.
Applications
 Example Applications

• Stabilization of enzymes for biocatalysis

• Dissolution and processing of biomass
• Natural product isolation and purification
• Reactor decontamination
 Stabilization of Biomolecules

0.12

0.105

Increase [NADH] (mol/L)x10-5

0.09

0.075

0.06

0.045

0.03

0.015

0
0 10 20 30 40 50 60 70
Tim e (hours)

Activity of alcohol dehydrogenase enzyme after storage in water

compared to standard (purple) and optimized (red) ionic liquids.
H2O Enzyme in water deactivated after 10 days
at room temperature.
AEFF-390
Enzyme in AEFF-390 retains activity after
AAFF-015
90 days at room temperature.
 Biomass Processing
• Ionic liquids can dissolve numerous polymers, including biological
macromolecules such as:-
• Cellulose (up to 10% wt. solutions)
• Lignin
• Proteins
• DNA/RNA
• Bioprocessing requires solvent to dissolve substrate without denaturing
enzyme.
• Ionic liquid can be designed accordingly.

O R
H
N R
N O R
R N H
H H O R
O
H O N
H N
H N O
O O
N
H
R
R
 Natural Product Extraction & Processing

80

70

60 H2O 0.15
50
Et2O 1.2

mg/mL
40

30 CHCl3 3.3
20
BMIm PF6 77.6
10

0
Water Diethyl ether Chloroform BMIm PF6

Morphine (free base) – solubility (gL-1)

• Solubility of natural products in ionic liquids often very much higher than
in conventional solvents.
• Can be used to extract high concentrations from natural sources, using
small extractor volumes.
 Natural Product Extraction & Processing

300

250

200

g/L
150 0°C
25°C
100

50

ABBF-001

ABBF-002

ABBF-003

ABBF-008

ABBF-010

ABBF-015

ABBF-357

ABBF-302

AEFF-002

AEFF-057

AEFF-357
• Dissolution of penicillin in ionic liquids – varies between solvent
formulations
• Solubility limit ranges from 20-270g/L
• Can design solvent to optimize extraction efficiency
 Natural Product Extraction & Processing

CH3
H

O
H3C O

O
H
H
O
CH3

• With support from MMV, Bioniqs has developed ionic liquids for artemisinin extraction,
from both wet and dry plant material.
• Extraction up to 4 times faster than in hexane
• Solubility in ionic liquids up to 110 gL-1 @ 25°C.
• Artemisinin may be recovered by adding water, precipitating and filtering off.
• Residual solvent content of recovered artemisinin <0.001%.
• Solvent may then be recycled and re-used Image provided courtesy of www.pp.clinet.fi
 Decontamination & Cleaning
250

200

Solubility (g/L)
150

100

50

BMImPF6
AEFF-015

AEFF-390

AFFF-015
AAJJ-015

AAJJ-057
AAFF-015

AAFF-302

AAFF-357

ABBF-008

ABBF-015

ABBF-049
Water

Solvent

• Solubility of two nitroaromatic pollutants in ionic liquids compared to water.

• Ionic liquid may be designed to dissolve one compound even in presence of
structurally similar materials.
 Decontamination & Cleaning

300

250

200

g/L
150 0°C
100 25°C

50

ABBF-001

ABBF-002

ABBF-003

ABBF-357

ABBF-302

AEFF-002
H2N O O

HN N
ILs designed to remove specified
OH contaminant (amoxicillin)
H
S All ILs tested dissolve contaminant to
HO >300g/L; several to >500g/L
 Ecotoxicity and Biodegradation

• ILs have been widely touted as “green” solvents

• recyclable
• non-flammable
• non-volatile

• BUT early imidazole-based ILs were

• poorly biodegradable
• toxic to micro-organisms
• may form hazardous hydrolysis products

• Biodegradability must be “built in” to an ionic liquid at the design stage.

 Biodegradation of Ionic Liquids
70.0 Mixed orgs #1 [m odified by dionex-user] 5m M t 0 ECD_1
µS
1 - 10.943

60.0
Na+ (standard)
50.0

ABBF+ 0 hrs
40.0 2 - 16.857

30.0

20.0 m in
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0
80.0 Mixed orgs #7 5m M t 66
µS

1 - 10.927

62.5

Na+ 48 hrs
50.0 NH4+
ABBF+ (98% removed)
2 - 13.047
37.5

3 - 14.673
4 - 16.863

20.0
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 8

• Ordinary soil organisms can grow on Bioniqs ionic liquids and completely
degrade them within 48 hours (above).
• Degradation products are water, carbon dioxide and ammonium ion.
• No significant toxic effects at concentrations below 80mM.
Synthesis Of Ionic Liquid
 O

O O Cl O Cl
C6H5NO2 EMImAl2Cl7
2-isomer 1-isomer

Scheme 1. Friedel-Crafts acetylation reaction of naphthalene.

 Comparison of organic solvents with ionic liquids

Plechkova, N. V.; Seddon K. R. Chem. Soc. Rev. 2008, 37, 123–150

Pravadoline,
a potential non-steroidal
anti-inflammatory drug
 Ionic Liquids in Organic Synthesis
• Catalytic
Friedel–Crafts
• Hydrogenetions
Alkoxycarbonylation
• Hydroformylations
Olefin dimerization
• Heck reactions
Diels-Alder
• Suzuki coupling
Oxidations
• Stille Coupling
Wittig reaction
Suzuki-Miyaura coupling reaction
Hydrogenation
 Summary

• Ionic liquids are not a panacea, but can offer major benefits in certain key
areas:-

• Can now compete on comparable cost footing with conventional solvents

for bulk applications.
• Reduced pollution and waste
• Improved process safety
• Enhanced efficiency of reaction and extraction processes

• Facilitate improved processes.

• Increased solubilities – smaller volumes
• Improved turnover rates and yields
• Stabilization of sensitive molecules
• Application to poorly soluble substrates
• https://www.youtube.com/watch?v=-MxMw8eFZAE
• https://www.youtube.com/watch?v=uYp9Hpboy0c
• https://www.youtube.com/watch?v=_XunLuNSaEM
• 10.1039/C3EE42099J

https://www.organic-chemistry.org/topics/ionic-liquids.shtm