Welton

Ionic liquids
Polarity and Solvation in Ionic

Liquids
Prof. Tom Welton
Imperial College
Polarity
Polarity of a liquid is defined as:
The sum of all possible specific and nonspecific interactions between the solvent and
a potential solute, except for those that lead to
a chemical reaction
When you heat a salt it will melt (e.g.,

NaCl, 801C).
The melt is composed of mobile ions (ionic
liquid).
Ionic liquids
Ionic liquid solutions
Make cation-solute and/or anion solute
interactions
Break solute-solute and cation-anion
interactions
These include:
Coulombic, dipolar, inductive and dispersive
forces, hydrogen-bonding etc..
Polarity
Polarity
Solvent-solute interactions are how liquids

change the behaviours of solutes.
There is no available measure of polarity.

All polarity scales are estimates.
Polarity is understood in qualitative terms.

The test of a polarity scale is usefulness.
Good quantitative understandings have
proved elusive.
Polarity
There is no concept of right and wrong
Polarity
There is no simple relationship

between different measures of
polarity.
There is no simple relationship

between different measures of
polarity.
"Polarities"
20
dipole moment(x 10 exp 30 / C m)
18
16
14
12
10
8
6
4
2
0
0
50
100
150
200
250
dielectric constant
Ionic liquid polarity

Ionic liquids have only moderate r
liquid
PC
DMSO
Acetonitrile
Acetone
[emim][OTf]
[emim][N(Tf)2]
[bmim][OTf]
[bmim][N(Tf)2]
Dichloromethane
THF
64.92
46.45
35.94
20.56
15.1
12.3
13.2
11.6
8.93
7.58

Ionic liquids have a wide range of dielectric constants.
Anion effect:
r is proportional to H-bond basicity
[HCO2]- > [C2OSO4]- [NO3]- >> [OTf]- > [BF4]- > [NTf2]- [PF6]-
Cation effect:
r is proportional to H-bond acidity
[(HO)C2NH3]+ > [C2NH3]+ > [CnCm im]+
Alkyl chain effect:

r is proportional to 1/chain length
Trends similar to those in molecular solvents
H. Weingrtner, Angew. Chem. Int. Ed., 2008, 47, 654.

r assumes that a liquid is
smooth and isotropic.
ILs are heterogeneous on
the nanoscale.*
Emission spectra of 2amino-7-nitrofluorene shows
the dye molecules occupying
distinct non-exchanging
environments.**
* Jos N. A. Canongia Lopes; Aglio A. H. Pdua; J.
Phys. Chem. B 2006, 110, 3330-3335.
** Mandal, P.; Sarkar, M.; Samanta, A. J. Phys. Chem. A
2004, 108, 9048.

r from dielectric spectroscopy fails to capture
the defining feature of ionic liquids the
translation of ions.
r from dielectric spectroscopy shows poor
agreement with:
Lack of kinetically active ion pairs in SN2 reactions
(see later).
Ionic association of Kosowers dye at equilibrium (see
later).
red/green (charged/nonpolar)
Empirical Polarity Scales
r from dielectric spectroscopy shows good

agreement with:
These have no solvent reorganisation on
timescale of measurement.
r from speed of sound together with densities and
heats of vapourization.*
Emission spectra of pyrene and PRODAN.
Timescales are important
Empirical polarity scales are based upon

measurements of some solvent dependent
property(ies)
e.g. spectra, rates or selectivities of reactions.
The property is selected to:

Be sensitive to as many solvent-solute interactions as
possible;
Have a wide range, so that a reasonable resolution of
results can be achieved.
Multiparameter scales are more helpful.

*Singh, T.; Kumar, A. J. Phys. Chem. B, 2008, 112, 12968.
**Baker, S. N.; Baker, G. A.; Kane M. A.; Bright, F. V. J. Phys. Chem. B, 2001, 105, 9663
Kamlet-Taft dyes
NH2
Kamlet-Taft Parameters
Et
Et
N
NO2
Reichardt's dye
4-nitroaniline
a = the hydrogen bond acidity of the

solvent: {-0.186(10.91-nR)-0.72p*}
b = the hydrogen bond basicity of the
solvent: {(1.035nNN+2.64-nNA)/2.80}
O-
A. R. Katritsky et al., Chem. Rev. 2004, 104, 175-198
NO2
N,N-diethyl-4-nitroaniline
p* = dipolarity/polarizability etc.:
{0.314(27.52-nNN)}
Solvent
p*
Solvent
p*
[bmpy] [OTf]
1.017
0.396
0.461
[bmpy] [OTf]
1.017
0.396
0.461
[bmpy] [N(Tf)2]
0.954
0.427
0.252
[bmpy] [N(Tf)2]
0.954
0.427
0.252
[bmim] [OTf]
1.006
0.625
0.464
[bmim] [OTf]
1.006
0.625
0.464
[bmim] [N(Tf)2]
0.984
0.617
0.243
[bmim] [N(Tf)2]
0.984
0.617
0.243
Acetone
0.704
0.202
0.539
Acetone
0.704
0.202
0.539
Methanol
0.730
1.050
0.610
Methanol
0.730
1.050
0.610
Dichloromethane
0.791
0.042
-0.014
Dichloromethane
0.791
0.042
-0.014
DMSO
1.000
0.000
0.760
DMSO
1.000
0.000
0.760
L. Crowhurst, P. R. Mawdsley, J. M. Perez-Arlandis, P. A. Salter and T. Welton, PCCP., 2003, 5, 2790 - 2794
Effect of the anions on a

The cation can H-bond to the anion
bmim + An
K1
bmim + solute
[bmpy] [OTf]
1.017
0.396
0.461
0.427
0.252
1.006
0.625
0.464
[bmim] [N(Tf)2]
0.984
0.617
0.243
Acetone
0.704
0.202
0.539
Methanol
0.730
1.050
0.610
[bmim ...solute]
Dichloromethane
0.791
0.042
-0.014
[bmim+][solute]
DMSO
1.000
0.000
0.760
bmim+..solute
K2 =
0.954
[bmim ][An ]
K2
p*
[bmpy] [N(Tf)2]
[bmim+...An-]
The cation can H-bond to the solute

+
Solvent
[bmim] [OTf]
bmim ...An
K1 =
Abraham model
The model is based on a theory of solvation that
describes the process in 3 steps
A cavity is generated in the solvent
The solvent reorganises around the cavity
The solute is introduced to the cavity and any solutesolvent interactions take place.
By studying a wide variety of solutes with known

properties a set of solvent parameters can be
generated.
The Abraham GC experiment

17 different ionic liquids, 8 from the same samples
used for the Kamlet-Taft experiment.
Prepared GC columns
Ran 36 probe solutes whose Abraham parameters are
known
Measured retention times at 40, 70 and 100 oC.
Multiple linear regression analysis was used to derive
the Abraham solvent parameters
Abraham Parameters
Log k = c+rR2+sp2H+aa2H+bb2H+l log L16
k = the property observed
c = constant
r = interactions with p- and n-electrons of the solute
s = dipolarity/polarizability
a = H-bond basicity
b = H-bond acidity
l = dispersion interactions
The Abraham parameters for

ionic liquids
a (hydrogen bond basicity) generally high and
depends mainly on anion.
b (hydrogen bond acidity) generally low and depends
on both cation and anion.
s (dipolarity/polarizability) values are high, showing
the influence of Coulombic interactions
s depends on both anion and cation, but no obvious
trend has been elucidated so far.
l (dispersion) nearly constant for all ionic liquids
studied
Do the Kamlet-Taft and Abraham

parameters agree?
Do the Kamlet-Taft and Abraham

parameters agree?
a and b are high in both models and depend mainly on the anion
b is low whereas a is high contradiction of the two scales

0.5
0.4
3.5
0.3
[N(Tf)2N]- ionic liquids
3
0.2
2.5
y = 3.7995x + 1.0823
R2 = 0.8578
[bmim]+ ionic liquids
0.1
0
0.25
-0.1
2
a
1.5
1
-0.2
0.5
-0.3
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
-0.4
0
0.2
0.25
0.3
0.35
0.4
0.45
0.5
-0.5

Reichardts dye agrees with solvatochromism of
merocyanine dyes.

Polarities derived from Reichardts dye agree
with:
Nucleophilic substitution reactions.
Byrne, R.; et al.. Phys. Chem. Chem. Phys. 2008, 10, 5919
Reichardts dye agrees with Kosowers z-scale.
Nu + CR3X
[NuCR3]+ + X-
Nu- + CR3X
NuCR3 + X-
Nu + [CR3X]+
[NuCR3]+ + X
Empirical Polarity Scales
Polarities derived from Reichardts dye do not

agree with:
GC measurements
solvatochromism of Fe(phen)2(CN)2 (phen = 1, 10phenanthroline);
fluorescence spectra of PRODAN and coumarin 153
Raman spectra of diphenylcyclopropane
the derived values were lower, and the relative

effects of changing cations or anions were
different
All of these are neutral probes!
Hydrogen bonding in ionic

liquids
H
The second assumption does not always hold:

it is important to consider the nature of the solute as
well as the solvent.
The effect of transferring a solute from a

molecular solvent to an ionic liquid depends
upon the charge on the solute.
Ionic liquids have a greater effect on charged solutes
than neutral solutes.
manifold of
C-H * MOs
C
if the response of the probe solute is the same as that

in some known solvent, then the polarities of the two
solvents are the same.
the effect of transferring from one solvent to another
is the same for all probes.
Empirical Polarity Scales for

ionic liquids
Theoretical investigations have shown the

importance of the Coulombic component of the
hydrogen bond.
C
Assumptions
filled
Cl p-AO
Therefore:
polarity scales based upon charged solutes correlate
well with the behaviours of other charged solutes
polarity scales based upon neutral solutes to correlate
well with the behaviours of other neutral solutes
P. A. Hunt,* B. Kirchner, T. Welton, Chem. Eur. J., 2006, 12, 6762-6775.
Nucleophilic substitutions
Bimolecular nucleophilic substitutions
have been used historically to investigate
solvent effects on the rates of reactions.
E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.
Bimolecular nucleophilic substitutions
have been used historically to investigate
solvent effects on the rates of reactions.
E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.
We have investigated the reaction of various
nucleophiles with methyl p-nitrobenzenesulfonate.
It can be followed by u.v. spectroscopy under
pseudo-first order conditions to give kobs.
1.7
1.5
Nu:
Me O S
NO2
O
253 nm
O
NuMe
(+)
O S
NO2
O
275 nm
Absorbance/ Arbitrary Units
O
(-)
1.3
1.1
0.9
0.7
0.5
0.3
0.1
-0.1240
250
260
270
280
290
300
wavelength/ nm
N. L. Lancaster and T. Welton J. Org. Chem., 2004, 69, 5986; J. Am. Chem. Soc., 2004,
126, 11549; N. L. Lancaster, P. A. Salter, T. Welton and G. B. Young, J. Org. Chem., 2002,
67, 8855; L. Crowhurst, R. Falcone, N. L. Lancaster, V. Llopis-Mestre and T. Welton, J. Org.
Chem., 2006, 71, 8847-8853 .
The isosbestic point shows that it is a simple

A to B reaction
Nucleophilic substitutions in
ionic liquids
It can be followed by u.v. spectroscopy under
pseudo-first order conditions.
kobs
We have used Linear Solvation Energy

Relationships (LSERs) used to analyse
the rates of nucleophilic substitution
reactions:
lnk2 = c + aa + bb + sp*
[Nu] / mol dm-3
k2 is derived from the linear plot of kobs vs [Nu]
ionic liquids
O
O
R3N +
Me
MeBu3N++ O2N
NO2
O-
X- + Me
LSER
R2
BuNH2 lnk2 = -8.77 + 4.57b + 6.32p* 0.93

Bu2NH lnk2 = -8.57 + 2.23b + 7.30p* 0.92
Bu3N lnk2 = 0.87 - 2.56a + 12.80p* 0.70
(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmpy][TfO], DCM, MeCN)
The change in the rate of the reaction is controlled by both

hydrogen bonding effects and generalised polarity effects.
MeBr + O2N
NO2
O-
R3N
ionic liquids
O
O
X-
LSER
R2
ClBrI-
lnk2 = 0.21 - 7.56a

lnk2 = 0.87 - 5.83a
lnk2 = 0.87 - 3.05a + 1.16b
0.99
0.97
0.95
(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmpy][TfO], DMSO, DCM, MeOH)
The change in the rate of the reaction is

dominated by specific hydrogen bonding effects.
10
ionic liquids
H3C
H3C
R3N +
ionic liquids
[CH3NR3]+
NO2
H3C
Cl- +
NO2
CH3Cl +
NO2
H3C
H3C
R3N
R2
LSER
NO2
R2
0.99
LSER
lnk2 = -2.74 6.54a
Cl-
BuNH2 lnk2 = -2.38 - 3.59a - 4.16b + 2.10p* 0.96

Bu2NH lnk2 = -2.66 - 2.79a - 5.01b + 2.89p* 0.99
Bu3N
lnk2 = -5.62 - 6.46b + 4.26p*
0.87
S
H3C
([bmim][Tf2N], [bm2im][Tf2N], [bmpy][Tf2N], [bmim][TfO], [bmpy][TfO], [Hbim][TfO])
(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmim][TfO], [bmpy][TfO], DCM,

MeCN, THF, MeOH)
Only ionic liquids appear in the LSER, because it is only in

ionic liquids that k2 can be derived.
The change in the rate of the reaction is controlled by both

hydrogen bonding effects and generalised polarity effects.
In molecular solvents the

reaction is not second order
[bm 2im+][Cl-] + [S+][NTf2-] in [bm2im][NTf2]
H3C
Cl- +
0.00025
CH3Cl +
NO2
0.0002
0.06
0.00015
0.05
0.0001
0.00005
THF
DCM
Propylene Carbonate
CH3CN
0.05
0.07
-1
K2 = 0.00363
0.03
0.02
0
0
0.01
0.02
0.03
0.04
0.06
[Cl ] (M)
k2 is derived from the linear plot of kobs vs [Nu]
0.01
0
0
NO2
H3C
0.04
M-1S-1
kobs (s )
kobs (s-1)
H3C
0.1
0.2
-
[Cl ] (M)
0.3
0.4
No reaction:
water
methanol
Negative order:
acetone
THF
DCM
Positive but not second order:
Propylene carbonate
Acetonitrile
DMSO
Second order:
Ionic liquids
11

mechanism is via ion pairs
H3C
H3C
Cl- +

mechanism is via ion pairs
CH3Cl +
NO2
DMSO
Acetonitrile
Propylene carbonate
H3C
S+
[R4N][Cl] + [S+][NTf2]
NO2
H3C
S
[R4N][NTf2] + [S+][Cl]
fast
metathesis
[S+][Cl]
+
[R4N][Cl]
slow
substitution
CH3Cl + S
Ionic liquids are highly dissociating

solvents.
{[A]+[B]-}
ionisation
molecule
CH3Cl +
NO2
acetone
THF
DCM
H3C
+
[R4N][Cl] + [S+][NTf2]
NO2
H3C
S
[R4N][NTf2] + [S+][Cl]
fast
metathesis
precipitation
The ionic liquid effect
A-B
Cl- +
ion pair
dissociation
association
[A]+ + [B]free solvated ions
Ion pairing is dominated by Coulombic

interactions and is usually highly
correlated with dielectric constants.
[S ][Cl]
+
[R4N][Cl]
CH3Cl + S
slow
substitution

Ionic liquids are far more dissociating than expected
from :
liquid
PC
DMSO
Acetonitrile
Acetone
[emim][OTf]
[emim][N(Tf)2]
[bmim][OTf]
[bmim][N(Tf)2]
Dichloromethane
THF
64.92
46.45
35.94
20.56
15.1
12.3
13.2
11.6
8.93
7.58
H. Weingrtner, Angew. Chem. Int. Ed., 2008, 47, 654.
12

reaction is not second order
H3C
Cl- +
CH3Cl +
NO2
H3C
NO2
H3C
0.06
0.05
THF
DCM
Propylene Carbonate
CH3CN
-1
kobs (s )
0.04
0.03
0.02
0.01
0
0
0.1
0.2
0.3
0.4
[Cl ] (M)
No reaction:
water
methanol
Negative order:
acetone
THF
DCM
Positive but not second order:
Propylene carbonate
Acetonitrile
DMSO
Second order:
Ionic liquids
Ion pairs
Solvent shared
(loose) ion pair
When you heat a salt it will melt (e.g.,

NaCl, 801C).
The melt is composed of mobile ions (ionic
liquid).
The ionic liquid effect
In a molecular solvent:
Solvent separated
ion pair
Ionic liquids
Contact (tight) ion

pair
Ionic liquids are super dissociating

solvents.
+
_
+
_
+
+ _
_
+
+ _
_
In an ionic liquid all ions are surrounded by

other ions.
+
_
+
_
+
_
+ _
_
+
+
_
+
+
+
_
Decreasing Ion Separation
_
+
+
_
+
_
_
+
_
+
_
+
_
+
_
+
_
_
+
_
+
_
_ +
+ _
_
+
+ _
+
+
_
+ _
+
+ _
_
_
_
+
+
+
+
_
_ +
+ _ + _
_
_
_
+
+
+
+
_
_
+ _
+ _
+
_
_
+
+
+ _
+
+
_
_ +
_
+
+
+ _ + _
_ + _
_
+
+
_ + _ + _
_ + _
_
+
+
_
+ _
+ _
_
+ _
+ _ +
_ + _ + _
_
+ _ + _ +
_
_
_
+
+
_
_ +
+
+
_
+ _ +
_
+ _
_ +
+
_
+
_
13
Charge screening of ion pairs in

ionic liquids (MD simulation)

Ionic liquids are super dissociating
solvents.
9 100% screening
Ion pairing in molecular solvents is dominated

by Coulombic interactions.
In an ionic liquid there is little difference
between these of the solute-solute and of the
solute-solvent interactions (highly screened).
Ion contacts that do form are rapidly disrupted
by the constant motion of the ions of the
solution (both solute and solvent).
3 55% screening
R. M. Lynden-Bell, Phys. Chem. Chem. Phys., 2010, 12, 1733.
Kosowers Dye
Kosowers Dye
1-butanol
3
2.5
2.5
Absorbance
Absorbance
MeCN
3
1.5
1
0.5
2
1.5
1
0.5
0
300
320
340
360
380
400
420
Wavelength / nm
440
460
480
500
300
320
340
360
380
400
420
440
460
480
500
Wavelength / nm
14
Kosowers Dye
Kosowers Z-scale
First comprehensive polarity scale
solvents using a solvatochromic dye.
Z-values of selective solvents
[C4C1im]NTf2
3
Liquid
Liquid
Water
94.6
MeCN
71.3
Methanol
83.6
DMSO
71.1
Ethanol
79.6
Acetone
65.5
[bmim][OTf]
76.0
DCM
64.7
0.5
[bmim][NTf2]
74.3
Ethyl acetate
59.4
[bmpy][NTf2]
73.3
Benzene
54.0
Absorbance
2.5
2
1.5
300
400
500
Wavelength / nm
Kosowers Dye
Kosowers dye
Z correlates well with ETN for both ionic

liquids and molecular solvents.
For the spectrum to be seen some [py]+

and I- ions must be in contact.
1
0.9
0.8
0.7
E TN
0.6
0.5
0.4
0.3
0.2
0.1
0
50
55
60
65
70
75
80
85
90
95
100
15
Kosowers Dye Absorbance
1-butanol
MeCN
30
20
25
Absorbance/Pathlength (cm-1)
18
16
14
12
10
8
6
20
15
10
4
2
0
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
Concentration / M
Concentration / M
Kosowers Dye
[C4C1im]NTf2
[C4C1im]OTf
30
20
18
25
20
15
10
16
14
12
10
8
6
4
2
0
0
0.02
0.04
0.06
0.08
0.1
Concentration / M
0.12
0.14
0.16
0.18
0.2
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
Concentration / M
16
Kosowers Dye Equilibrium

Model
Beer-Lambert Law
A = cl
Consider the simple equilibrium of ion

association:
= molar absorptivity (constant)

c = concentration
l = path length
Non-linear A vs c indicates that there is an

equilibrium.
the following equilibrium model was

derived:
CIP = (CT - 0.5/K) 0.5*SQRT{4*CT/K + 1/(K2)}
Kosowers Dye
1400
1400
1200
1200
1000
1000
800
K=1000
K=100
K=50
600
K=10
K=1
400
200
Extinction coefficient

Model
800
DCE
1-butanol
600
MeCN
400
200
0
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
Concentration, M
0.04
0.045
0.05
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
0.05
Concentration / M
= A/cTl
CIP = (CT - 0.5/K) 0.5*SQRT{4*CT/K + 1/(K2)}
17
Kosowers Dye in ionic liquids
Kosowers Dye in ionic liquids
140
160
140
120
y = 681.33x + 5.8247
120
100
y = 592.94x + 5.5254
80
[bmim]BF4
60
[bmim]OTf
40
Extinction
coeffcient
100
80
[bmpy]NTf2
[bmim]NTf2
60
40
20
20
0
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
Concentration / M
Concentration / M
Kosowers Dye
What is the reaction?

This is a metathesis reaction.
60
55
50
45
40
35
30
K=1
25
20
15
10
5
0
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
concentration, M
K=1
G = -RTlnK = 0
18

Model

Model
Two energies per complex Energy of metathesis not unambiguous
AVR: calculated from the average energy per complex
MIN: calculated from the lowest energy per complex
MAX: calculated from the highest energy per complex
Simplest possible model for metathesis
Two lowest energy structures for each complex on B3LYP/6-31++G(d,p)

level of theory with small core ECP for iodide
Singlepoint calculations using zero-point energy (+Z) and basis set
superposition error (+B) correction on B3LYP level
Singlepoint MP2 energies on B3LYP geometry
AVR
MIN
MAX
DFT
22.13
23.09
21.16
DFT+Z
19.60
18.37
20.83
DFT+Z+B
20.02
18.40
21.64
MP2
3.95
-2.83
10.73
MP2+Z
1.42
-4.90
7.75
On highest level of theory: Metathesis energy neutral within simple model

system
Ion solvation
All ions are randomly associated
Dynamic system prevents long-lived ion
contacts
There are no special ion pairs in solutions
of Kosowers dye in ionic liquids.
Acknowledgements
Dr Patricia Hunt (theory)

Dr Lorna Crowhurst (polarity)
Dr Jason P. Hallett (kinetics)
Dr Patricia Hunt (theory)
Dr Juan Perez-Arlandis (polarity and kinetics)
Dr Guiseppe Ranieri (kinetics)
Mr Matthew Lui (polarity)
Mr Heiko Niedermeyer (theory)
Leverhulme Trust, Kodak Foundation, EPSRC, ERC

(funding)
19

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Ionic liquids

Polarity and Solvation in Ionic

When you heat a salt it will melt (e.g.,

Solvent-solute interactions are how liquids

There is no available measure of polarity.

Polarity is understood in qualitative terms.

There is no concept of right and wrong

There is no simple relationship

There is no simple relationship

dipole moment(x 10 exp 30 / C m)

Ionic liquid polarity

Ionic liquid polarity

Alkyl chain effect:

Trends similar to those in molecular solvents

H. Weingrtner, Angew. Chem. Int. Ed., 2008, 47, 654.

Ionic liquid polarity

Ionic liquid polarity

Ionic liquid polarity

Empirical Polarity Scales

r from dielectric spectroscopy shows good

Timescales are important

Empirical polarity scales are based upon

The property is selected to:

Multiparameter scales are more helpful.

a = the hydrogen bond acidity of the

A. R. Katritsky et al., Chem. Rev. 2004, 104, 175-198

Ionic liquid polarity

Ionic liquid polarity

Effect of the anions on a

The cation can H-bond to the solute

Ionic liquid polarity

By studying a wide variety of solutes with known

The Abraham GC experiment

The Abraham parameters for

Do the Kamlet-Taft and Abraham

Do the Kamlet-Taft and Abraham

b is low whereas a is high contradiction of the two scales

[N(Tf)2N]- ionic liquids

[bmim]+ ionic liquids

Ionic liquid polarity

Ionic liquid polarity

Reichardts dye agrees with Kosowers z-scale.

Ionic liquid polarity

Empirical Polarity Scales

Polarities derived from Reichardts dye do not

the derived values were lower, and the relative

Hydrogen bonding in ionic

The second assumption does not always hold:

The effect of transferring a solute from a

if the response of the probe solute is the same as that

Empirical Polarity Scales for

Theoretical investigations have shown the

P. A. Hunt,* B. Kirchner, T. Welton, Chem. Eur. J., 2006, 12, 6762-6775.

E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.

E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.

Absorbance/ Arbitrary Units

The isosbestic point shows that it is a simple

We have used Linear Solvation Energy

[Nu] / mol dm-3

k2 is derived from the linear plot of kobs vs [Nu]

BuNH2 lnk2 = -8.77 + 4.57b + 6.32p* 0.93

The change in the rate of the reaction is controlled by both

lnk2 = 0.21 - 7.56a