1
The transfer of neutral molecules, ions and ionic species from water to
benzonitrile; comparison with nitrobenzene.
Michael H Abraham a * and William E. Acree, Jr b
a
Department of Chemistry, University College London, 20 Gordon St, London WC1H
0AJ, UK. Email: m.h.abraham@ucl.ac.uk
b
Department of Chemistry, 1155 Union Circle Drive #305070, University of North
Texas, Denton, TX 76203-5017, USA Email: bill.acree@unt.edu
ABSTRACT
Equations have been constructed for the transfer of 64 neutral solutes from water and
from the gas phase to the solvent benzonitrile. The equations contain five descriptors and
can be used to predict further values of the water-benzonitrile and gas-benzonitrile
partition coefficients for a wide range of solutes. The water-benzonitrile equation has
been extended to include ions and ionic species derived from acids by loss of a proton
and bases by acceptance of a proton. Only two further descriptors are needed, one for
anions and one for cations. A previous equation for transfer of neutral solutes from water
to nitrobenzene has also been extended to include ions and ionic species. Comparison of
the equations for transfer to benzonitrile and to nitrobenzene shows that the two solvents
behave quite similarly, although benzonitrile as a solvent is a stronger hydrogen bond
base.
* Corresponding author. Tel.: 020-7679-4639; fax: 020-7679-7463. E-mail address:
m.h.abraham@ucl.ac.uk (M. H. Abraham)
1. Introduction
Benzonitrile is a useful extraction solvent for hydrocarbons and fatty acids and as a
general solvent in the perfumery and pharmaceutical industries. Many properties of
1
2
benzonitrile are very similar to those of nitrobenzene, see Table 1, including those that
influence their solvent character. The Kamlet-Taft parameters π*1 the solvent dipolaritypolarizability, α1 the solvent hydrogen bond acidity and β1 the solvent hydrogen bond
basicity are important as regards solubility and partition of neutral molecules [1,2], and
the solvent dielectric constant ε is a key parameter in studies of electrolytes. In spite of
the similarity of these solvent parameters, there has been little comparison of the
solubility properties of benzonitrile and nitrobenzene.
Table 1
Some properties of benzonitrile and nitrobenzene
Property
Benzonitrile
Nitrobenzene
Melting point, oC
-13
+6
Boiling point, oC
205
211
Refractive index at 20oC
1.5279
1.5562
Density at 20oC
0.9955
1.2037
Dielectric constant at 25oC
25.19
34.82
Reichardt ET
42.0
42.0
Dipole moment
4.18
4.22
Kamlet-Taft π*1
0.90
1.01
Kamlet-Taft α1
0.00
0.00
Kamlet-Taft β1
0.37
0.30
In previous studies [3-5], we have shown that two general equations, Eqs. (1) and
(2), can be used for the transfer of neutral solutes from water to organic solvents and
from the gas phase to organic solvents. The dependent variable in Eq. (1) is log P, where
P is the molar water to solvent partition coefficient for a series of solutes, and in Eq. (2)
is log K where K is the dimensionless gas phase to water partition coefficient for a series
of solutes.
Log P = c + e E + s S + a A + b B + v V
(1)
2
3
Log K = c + e E + s S + a A + b B + l L
(2)
In Eq. (1) and (2) the independent variables, or descriptors, are properties of the neutral
solutes as follows [3-5]: E is the solute excess molar refraction in cm3 mol-1/10, S is the
solute dipolarity/polarizability, A is the overall solute hydrogen bond acidity, B is the
overall solute hydrogen bond basicity, V is McGowan’s characteristic molecular volume
in cm3 mol-1/100 and L is the logarithm of the gas to hexadecane partition coefficient at
298 K. Examples of the coefficients in Eq. 1 are shown in Table 1 for partition from
water to a number of solvents [5].
Table 1.
Coefficients in Eq. (1) and Eq. (3) for partitions from water to solvents.
Solvent
c
e
s
a
b
v
Methanol
0.276
0.334
-0.714
0.243
-3.320
3.549
Ethanol
0.222
0.471
-1.035
0.326
-3.596
3.857
Propanone
0.313
0.312
-0.121
-0.608
-4.753
3.942
Nitromethane
0.023
-0.091
0.793
-1.463
-4.364
3.460
Acetonitrile
0.413
0.077
0.326
-1.566
-4.391
3.364
Benzene
0.142
0.464
-0.588
-3.099
-4.625
4.491
Chlorobenzene
0.065
0.381
-0.521
-3.183
-4.700
4.614
Nitrobenzene
-0.152
0.525
0.081
-2.332
-4.494
4.187
Benzonitrile
0.097
0.285
0.059
-1.605
-4.562
4.028
c
e
s
a
b
l
Methanol
-0.039
-0.338
1.317
3.826
1.396
0.773
Ethanol
0.017
-0.232
0.867
3.894
1.192
0.846
Propanone
0.127
-0.387
1.733
3.060
0.000
0.866
Nitromethane
-0.340
-0.297
2.689
2.193
0.514
0.728
-0.007
-0.595
2.461
2.085
0.418
0.738
0.107
-0.313
1.053
0.457
0.169
1.020
Solvent
Acetonitrile
Benzene
3
4
Chlorobenzene
Nitrobenzene
Benzonitrile
0.064
-0.399
1.151
0.313
0.171
1.032
-0.296
-0.075
0.092
-0.341
1.707
1.798
1.147
2.030
0.443
0.291
0.912
0.880
Recently, we have shown [6-10] that Eq. (1) can be extended to include partition
coefficients of ions and of ionic species; we use the latter term to describe anions derived
from acids by loss of a proton, and cations derived from bases by acceptance of a proton.
The descriptors for anions and cations are E, S, A, B, and V on exactly the same scales as
-
for neutral molecules, together with an additional descriptor, J , for anions and an
-
additional descriptor, J+, for cations. The complementary solvent coefficients are j and
j+ so that Eq. (1) is transformed into Eq. (3),
- Log P = c + e E + s S + a A + b B + v V + j+ J+ + j J
(3)
For anions j+ = 0, for cations j = 0, and for neutral solutes j+ = j = 0 so that Eq. (3) then
reverts to Eq. (1). Values of the solvent j+ and j coefficients are in Table 1 [6-10], and
descriptors for a number ions and ionic species are in Table 2. In the present context, it is
of some interest that we were not able to characterize the solvent nitrobenzene
completely and could not obtain the j+ coefficient for anions. However, we aim to
compare equations for log K and log P for neutral compounds as between benzonitrile
and nitrobenzene and hope to be able to characterize benzonitrile as regards partition of
ions and ionic species.
2. Methodology
The experimental data that we use for neutral solutes refer either to log P values for
“practical”
partition
between
benzonitrile-saturated
water
and
water-saturated
benzonitrile, or to the Raoult’s law infinite dilution activity coefficient, γsolute, or
4
5
Henry’s law constants, KHenry, for solutes dissolved in (dry) benzonitrile. The infinite
dilution activity coefficients and Henry’s law constants need to be converted to log K
values through Eq. 4 and 5.
log K  log (
log K  log (
RT


solute
o
Psolute Vsolvent
RT
K Henry Vsolvent
)
(4)
(5)
)
Log P values for partition from water to benzonitrile can be converted to log K values
through Eq. (6).
Log P = log K – log Kw
(6)
In Eq. 4 and 5, R is the universal gas constant, T is the system temperature, Psoluteo is the
vapor pressure of the solute at T, and Vsolvent is the molar volume of the solvent. The
calculation of log P requires knowledge of the solute’s dimensionless gas phase partition
coefficient into water, Kw, which is available for most of the solutes being studied. Eq. 6
can also be used in reverse to convert log P into log K values for transfer from the gas
phase into (wet) benzonitrile.
In the case of electrolytes, partition coefficients, or the equivalent Gibbs energies of
transfer are sometimes available from water to dry solvents, mostly determined through
solubility measurements. The method is much more complex than for neutral solutes, and
requires knowledge of the ion-pair association constant in the organic solvent as well as
an estimation of the mean ionic activity coefficient of the electrolyte in the organic
solvent. In addition, the presence of hydrates or solvates will lead to errors in any
determined log P value. Once log P for a neutral combination of ions has been obtained,
it is necessary to use some particular convention to obtain values for the individual ions.
We use the convention that log P (Ph4P+ or Ph4As+) = log P (Ph4B ), the well-known
TATB assumption.
5
6
For ionic species such as protonated amine cations or carboxylate anions, it is
possible to obtain log P values through a quite different procedure based on the variation
of pKa with solvent. For carboxylate anions, Eq. (7) can be used.
Log P(A-) = log P(HA) – log P(H+) + pKa(aq) – pKa(s)
(7)
P(A-) is the partition coefficient from water to a solvent of the carboxylate anion, P(HA)
is the partition coefficient of the neutral carboxylic acid, P(H+) is the partition coefficient
of the hydrogen ion, and pKa(aq) and pKa(s) are the pKa values of the carboxylic acid in
water and the given solvent. The corresponding equation for partition of a protonated
amine is Eq. (8).
Log P(BH+) = log P(B) + log P(H+) - pKa(aq) + pKa(s)
(8)
In Eq. 8, BH+ refers to the protonated amine and B to the neutral amine. If the TATB
convention is to apply to log P(A-) and to log P(BH+) then log P(H+) values must be set
out must be on this convention as well.
3. Results and discussion
The data that we have collected on solubility or partition of non-electrolytes is in
Table 2 [11-30]. We distinguish, for the moment, data that refers to dry benzonitrile and
to wet (that is water-saturated) benzonitrile, and include in Table 2 an ‘indicator
variable’, I, for dry or wet benzonitrile.
Table 2
Values of log K and of log P for gas to benzonitrile or water to benzonitrile partition. at
25oC.
Solute
Argon
Carbon monoxide
Sulfur dioxide
Sulfur hexafluoride
Ref
log K
log P
I
log Kw
11 -0.825
-1.467
0.642
29 -0.789
-1.620
0.831
22,30
1.902
1.530
0.372
11 -0.521
-2.230
1.709
6
1
1
1
1
7
Carbon disulfide
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane
2-Methylpentane
2,4-Dimethylpentane
2,5-Dimethylhexane
2,3,4-Trimethylpentane
Cyclohexane
Ethylcyclohexane
Ethene
Isoprene
Pent-1-ene
2-Methylbut-2-ene
Hex-1-ene
trans-Penta-1,3-diene
Cyclohexene
Pent-1-yne
Chloromethane
Dichloromethane
Chloroethane
t-Butyl chloride
Bromoethane
t-Butyl bromide
Iodomethane
Iodoethane
Dioxane
Butanone
Methanol
Ethanol
Propionitrile
Nitromethane
Dimethylamine
Triethylamine
Benzene
Toluene
Fluorobenzene
Chlorobenzene
1,2-Dichlorobenzene
13
12
12
12
19
19
19
19
19
19
19
19
19
19
19
11
20
13
20
16
16
16
16
22
13
12
14
12
14
13
12
18
18
13
18
12
18
23
15
20
18
17
17
17
2.332
0.378
0.816
1.324
1.834
2.280
2.740
3.194
3.640
2.120
2.367
2.810
2.926
2.583
3.338
0.330
2.199
1.910
2.119
2.216
2.387
2.896
2.428
1.606
2.773
2.113
2.307
2.498
2.671
2.500
2.936
3.772
3.356
2.480
2.817
3.532
3.609
2.054
2.977
3.184
3.684
3.324
4.124
5.000
7
-0.150
-1.336
-1.436
-1.503
-1.704
-1.821
-1.961
-2.109
-2.150
-1.840
-2.080
-2.020
-1.880
-0.900
-1.580
-0.940
-0.500
-1.230
-0.960
-1.160
-0.360
-0.270
-0.010
0.400
0.960
0.460
-0.800
0.540
-0.620
0.650
0.540
3.710
2.720
3.740
3.670
2.820
2.950
3.150
2.360
0.630
0.650
0.590
0.820
1.000
2.482
1.714
2.252
2.827
3.538
4.101
4.701
5.303
5.790
3.960
4.447
4.830
4.806
3.483
4.918
1.270
2.699
3.140
3.079
3.376
2.747
3.166
2.438
1.206
1.813
1.653
3.107
1.958
3.291
1.850
2.396
0.062
0.636
-1.260
-0.853
0.712
0.659
-1.096
0.617
2.554
3.034
2.734
3.304
4.000
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
8
Iodobenzene
Benzonitrile
Benzyl alcohol
Anthracene
Pyrene
Ethanol (wet)
Propan-1-ol (wet)
Ethyl acetate (wet)
Butyl acetate (wet)
Propanone (wet)
Acetonitrile (wet)
Proprionitrile (wet)
N,N-Dimethylformamide(wet)
N-Methylformamide(wet)
Formamide(wet)
DMSO (wet)
a
Taking γsolute as unity.
17
5.118
5.357
5.864
8.370
9.600
2.943
3.273
3.140
4.090
2.843
2.933
3.573
5.002
5.833
5.763
6.273
a
21
16
17
28
28
24
24
27
25
25
26
26
26
27
1.280
3.090
5.100
3.030
3.500
3.670
3.560
2.160
1.940
2.830
2.850
2.820
5.730
6.570
7.470
7.410
3.838
2.267
0.764
5.340
6.100
-0.727
-0.287
0.980
2.150
0.013
0.083
0.753
-0.728
-0.737
-1.707
-1.137
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
2
In order to ascertain if partitions into wet and dry benzonitrile are essentially the same,
we applied Eq. 1 to the log P values in Table 2, and included the indicator variable, I. If
the coefficient of the indicator variable is not statistically significant, then log P values
into wet and dry benzonitrile can be combined in the simple Eq. 1. The resulting
equations with and without the indicator variable are Eq. 9 and 10; N is the number of
data points, i.e. compounds, SD is the regression standard deviation, R is the correlation
coefficient and F is the F-statistic. The leave-one-out statistics are PRESS and Q, and
PDS is the predictive standard deviation [31]. The coefficient of I is -0.003 with an SD =
0.074 and so is statistically not significant. The suggested equation, Eq. 10, should be
capable of predicting further values of log P to about 0.18 log units.
Log P = 0.099 + 0.283 E + 0.061 S - 1.604 A - 4.562 B + 4.029 V - 0.003 I
(9)
N = 64 SD = 0.154 R2 = 0.994 F = 1629.9
PRESS = 1.9111 Q2 = 0.993 PSD = 0.183
log P = 0.097 + 0.285 E + 0.059 S - 1.605 A - 4.562 B + 4.028 V
8
(10)
9
N = 64 S = 0.153 R2 = 0.994 F = 1990.1
PRESS = 1.8621 Q2 = 0.992 PSD = 0.179
It is also clear from the statistics and coefficients in Eq. 9 and 10 that the indicator
variable is redundant and that log P values into wet and dry benzonitrile can be combined
as in Eq. 10. A similar analysis of log K values leads to I = 0.006 with SD = 0.055 so
again the indicator variable is not statistically significant. The equation for log K is then
Eq. 11, capable of predicting log K values to about 0.14 log unit.
log Ks = - 0.075 - 0.341 E + 1.798 S + 2.030 A + 0.291 B + 0.880 L
(11)
N = 64 S = 0.114 R2 = 0.996 F = 3172.8
PRESS = 1.1058 Q2 = 0.995 PSD = 0.138
Comparison of coefficients in Eq. 10 and 11 with those for nitrobenzene, Table 2,
suggests that the main difference is that benzonitrile is an appreciably stronger hydrogen
bond base, with a-coefficients -1.605 (benzonitrile) and -2.328 (nitrobenzene) in Eq. 1,
and 2.030 (benzonitrile) and 1.147 (nitrobenzene) in Eq. 2. Interestingly, acetonitrile and
nitromethane have almost the same hydrogen bond basicity, see Table 2.
Once coefficients in Eq. 1 have been established for any solvent, it is then possible
to attempt to obtain an equation on the lines of Eq. 3 for the partition of ions and ionic
species. Marcus [32, 33] records Gibbs energies of transfer of a few ions from water to
benzonitrile, but these are either calculated in some way, or are observed values, but not
on the TATB convention. However, Gibbs energies of transfer on the TATB convention
were subsequently determined by Namor and Ponce [34, 35] from measurements of
solubilities of 1:1 electrolytes. These yield directly log P values for single ions. A few
Gibbs energies of transfer of 1:1 electrolytes were also determined by Abraham [36].
Chmurzyński and Wawrzyniak [37] have determined pKa values for pyridine-N-oxide
and the three methylpyridine-N-oxides in benzonitrile and in water. These can be used in
Eq. 8 provided that log P(H+) and log P for the neutral pyridine-N-oxides can be
established. The latter can be estimated from the known descriptors for pyridine-N-oxides
9
10
and the coefficients in Eq. 10, but log P(H+) remains to be found. We obtained a value
for log P(H+) that gave self-consistent values for log P for the protonated pyridine-Noxides and log P for the various cations. Details of the observed and calculated single-ion
log P values are in Table 3; the descriptors for the ions are as before[6-10].
Table 3.
Calculated and observed values of log P for transfer from water to benzonitrile.
Ion
Na+
Log P
Calc
Obs
-2.46
Ref
K+
-2.30
-2.44 32
Rb+
-2.21
-2.67 33
-2.08
-2.27 33
Et4N
0.80
0.84 33
Pr4N+
Pyridine-N-oxideH+
2-Methylpyridine-N-oxideH+
3.01
3.26 33
-1.42
-1.06
-1.66 36
-1.06 36
3-Methylpyridine-N-oxideH+
-0.87
-0.97 36
4-Methylpyridine-N-oxideH+
-0.27
0.06 36
6.48
6.41 33
6.39
6.40 34
Cs+
+
Ph4P+
Ph4As
F
Cl
Br-
+
-9.99
-8.98
-8.70 35
-6.55
-6.42 33
I-
-3.88
-4.30 33
ClO4BPh4
-2.00
-2.31 33
6.13
6.18 33
We find that log P(H+) = -8.17 in order to include the pyridine-N-oxideH+ ions, and that
j+ = -2.729 and j = 0.136. Thus partitions of neutral molecules, ions and ionic species
can all be correlated in one equation,
10
11
Log P = 0.097 + 0.285 E + 0.059 S - 1.605 A - 4.562 B + 4.028 V -2.729 J+
-
+ 0.136 J
(12)
Log P values for the 16 ions in Table 3 are fitted by Eq. 12 with SD = 0.241 log units,
which is quite reasonable. Some values of the coefficients j+ and j for partitions of ions
to other solvents are in Table 4 for comparison.
Table 4
Values of the solvent coefficients j+ and j
j+
-
Methanol
-2.609
j
3.027
Ethanol
-3.170
3.085
Ethylene glycol
-1.300
2.363
-2.288
-1.989
0.078
0.341
Benzonitrile
-2.243
-2.729
0.101
0.136
Nitrobenzene
-2.728
0.534
-3.387
0.132
Solvent
Propanone
Propylene carbonate
Acetonitrile
DMSO
It would be especially interesting to be able to compare the ionic coefficients j+ and
j for partition to benzonitrile with those for partition to nitrobenzene. Marcus [33] listed
data for transfer of a few ions to nitrobenzene, but later on Namor et al. [38] used the
solubility method to obtain data for a range of ions. Herrera et al. [39], rather oddly,
repeated the work of Namor et al. [38] but added nothing of significance and so we just
use the data of Namor et al. [38] for transfer to dry nitrobenzene. Gérin and Fresco [40]
11
12
used a direct method to determine partition coefficients of a series of trialkylammonium
chlorides, bromides, iodides and perchlorates to wet nitrobenzene. Their results are quite
compatible with those of Namor et al. [38], and indicates that transfers of ions to wet and
dry nitrobenzene can be combined in the same equations. An electrochemical method
was used by Osakai et al. [41] to obtain partition coefficients for a series of
alkylammonium ions to wet nitrobenzene; we have descriptors for some, but not all of the
alkylammonium ions. The data of Osakai et al. [41] are relative, and we found that
addition of 0.633 log units to the log P values brought them on to the TATB scale used
by Namor et al. [38]. Chmurzyński et al. [42] have determined pKa values for protonated
pyridine and a number of protonated pyridine-N-oxides in dry nitrobenzene. We can then
use Eq. 8 to obtain log P values for these ionic species. Values of log P(B) for the neutral
bases were estimated using the coefficients for transfer to nitrobenzene in Eq. 1 as listed
in Table 1, and descriptors for the neutral bases [10]. The value of log P(H+) was found
by trial and error to be -6.43, in quite good agreement with a value of -5.70 listed by
Marcus [33].
Details of all the log P values for ions and ionic species are in Table 5, together with
calculated values through Eq. 3; Me4N+ and 4-Methylpyridine-N-oxideH+ are
considerable outliers, and if they are left out, SD = 0.331 with j+ -2.728 and j = 0.534
for 27 ions. The final equation for the correlation transfer of neutral compounds, ion and
ionic species from water to wet or dry nitrobenzene is thus Eq. 13.
Log P = -0.152 + 0.525 E + 0.081 S – 2.332 A - 4.494 B + 4.187 V -2.728 J+
-
+ 0.534 J
(13)
Table 5
Calculated and observed values of log P for transfer from water to nitrobenzene
Ion
+
Na
K+
Rb+
Log P
Calc a
-3.54
-3.35
-3.14
12
Obs
Ref
-3.67
-3.37
38
38
13
Cs+
EtNH3+
PrNH3+
BuNH3+
Me2NH2+
Et2NH2+
Pr2NH2+
Me3NH+
Et3NH+
Pr3NH+
Bu3NH
Me4N+
Et4N+
Pr4N+
PyridineH+
Pyridine-N-oxideH+
2-Methylpyridine-N-oxideH+
3-Methylpyridine-N-oxideH+
4-Methylpyridine-N-oxideH+
Ph4P+
Ph4As+
-3.07
-2.91
-2.31
-1.89
-2.52
-1.46
-0.40
-1.43
-0.31
0.95
2.03
(-1.86)b
0.42
2.78
-2.42
-2.47
-2.14
-1.95
(-1.28) b
7.31
7.21
-3.12
-2.71
-2.21
-1.75
-2.33
-1.66
-0.70
-1.50
-0.40
0.92
2.38
-0.70
0.84
2.87
-2.75
-2.21
-1.89
-2.17
-2.84
6.54
6.32
38
41
41
41
41
41
41
41
41
40
40
38
38
38
42
42
42
42
42
38
38
F
-9.04
Cl
Br
I
-7.88
-7.60
38, 40
-5.90
-3.31
-6.10
-3.70
38, 40
38, 40
-1.52
-1.70
38, 40
0.59
38
6.32
38
ClO4
-
0.50
Picrate
6.71
Ph4B
a
From Eq. 13. b Not used in the calculations.
The SD value of 0.329 log units for transfer of ions from water to nitrobenzene is not
as good as usual for such transfers. Furthermore, Eq. 19 leads to poor agreement of
calculated and observed values for the TATB ions.
13
14
In addition to log P values for ions obtained from solubility or distribution
experiments, there are a number of log P values from electrochemical experiments [4348]. Unfortunately, there is no consistency between the two sets of log P values. In Table
6 we list log P values obtained by the electrochemical method for those ions for which
we can calculate values from Eq. 13. In most cases, our calculated values are more
negative than those observed [43-48]. We have no explanation as to why log P values
obtained from solubility measurements, from direct partition experiments, and from the
variation of pKa with solvent yield reasonably self-consistent values, and yet log P values
obtained from electrochemical methods do not appear to agree with the first set.
The ‘ionic’ descriptors, j+ and j for partition into benzonitrile, Eq. 12, and into
nitrobenzene, Eq. 13, are quite close to each other. Comparison of these coefficients for a
range of solvents, see Table 4, shows that for partition to hydroxylic solvents j+ is always
large and negative and j is large and positive. For partition to the polar or moderately
polar aprotic solvents, j+ is again always large and negative but j is very small and
positive. The coefficients for benzonitrile and nitrobenzene thus fit into the general
pattern for other solvents.
Table 6
Values of log P for transfer of ions and ionic species from water to nitrobenzene
obtained by electrochemical methods; comparison with calculated values through Eq. 13.
Ion
Log P
BuNH3
Me4N+
Calc a
-1.89
-1.86
Cl
Br
I
ClO4
CN
+
Log P
Obs
-2.86
-1.21
Ref
48
48
Log P
Obs
Ref
47
47
-7.88
-
-5.90
-3.31
-2.94
48
-5.26
-3.15
-1.51
-0.91
48
-0.88
47
-6.47
-5.19
44
<-6.0
47
14
Log P
Obs
Ref
15
-
-5.90
4.70
44
Phenoxide
-4.90
-3.62
45
-3.58
43
2-Nitrophenoxide
3-Nitrophenoxide
4-Nitrophenoxide
-4.39
-2.59
45
-2.52
43
-4.34
-3.54
45
-3.45
-3.81
45
-
-3.08
-1.54
45
-
-3.33
-2.48
45
0.50
0.53
45
-7.25
-3.72
45
-4.73
46
-4.78
46
N3
2,4-Dinitrophenoxide
2,5-Dinitrophenoxide
Picrate
Benzoate
4-Methylbenzoate
3-Chlorobenzoate
4-Chlorobenzoic
4-Bromobenzoate
3-Iodobenzoate
4-Iodobenzoate
2-Nitrobenzoate
3-Nitrobenzoate
4-Nitrobenzoate
Acetate
Propanoate
Butanoate
Pentanoate
Hexanoate
Heptanoate
Octanoate
Fluoroacetate
Dichloroacetate
a
From Eq. 13
-6.82
-5.52
-2.70
45
-5.56
-2.17
45
-3.68
46
-5.28
-2.13
45
-3.50
46
-2.98
46
-2.98
46
-6.86
-4.20
46
-6.08
-3.50
46
-6.09
-3.50
46
-4.66
-4.86
-2.48
45
-9.96
-5.27
44
-5.10
43
-9.47
-4.90
44
-4.78
43
-9.38
-4.60
44
-4.88
43
-8.72
-3.91
44
-4.70
43
-7.54
-3.17
44
-4.02
43
-7.20
-2.49
44
-3.13
43
-4.73
46
-6.74
-2.21
44
-2.41
43
-4.20
46
-8.83
-5.24
44
-5.77
-4.63
44
15
16
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18