Fluid Phase Equilibria 250 (2006) 165172

The effect of temperature on the solubility of benzoic

acid derivatives in water
Jia Qing-Zhu
a,b,
, Ma Pei-Sheng
a
, Zhou Huan
b
, Xia Shu-Qian
a
,
Wang Qiang
a
, Qiao Yan
a
a
College of Chemical Engineering, Tianjin University, Tianjin 300072, P.R. China
b
College of Marine Science and Engineering, Tianjin University of Science and Technology, Tianjin 300457, P.R. China
Received 10 March 2006; received in revised form 17 October 2006; accepted 18 October 2006
Abstract
Using a laser monitoring observation technique, solubilities of o-nitro-benzoic acid, p-hydro-benzoic acid, p-methyl-benzoic acid and m-methyl-
benzoic acid in water have been measured in the temperature range 290.15323.15 K. The experimental data are regressed with the Wilson equation
and the H equation. The experimental results show that solubilities of these compounds in the range of 10
4
10
5
mole fraction in water, increase
signicantly with temperature. Except for o-nitro-benzoic acid, the solubility data are described adequately with the Wilson equation. The H
equation gives good agreement with all experimental data. The results indicate that the molecular structure and interactions affect the solubilities
signicantly.
2006 Elsevier B.V. All rights reserved.
Keywords: o-Nitro-benzoic acid; p-Hydro-benzoic acid; p-Methyl-benzoic acid; m-Methyl-benzoic acid; Solubility in water; Wilson equation; H equation
1. Introduction
The physicalchemical properties of organic substances
are essential for understanding their environmental behavior.
Among these properties, aqueous solubility plays a prominent
role in the prediction of the environmental fate of chemi-
cals. Solubility in water affects processes, such as evaporation,
absorption and bioaccumulation [1,2].
Although there have been many studies of the solubility of
organic compounds in water, data on its temperature dependence
are scare or unavailable [3]. However, such temperature depen-
dence of physicalchemical properties is important to improve
the predictive capability of environmental models [4]. In fact,
differences in temperature, seasonally diurnally, and between
different regions of the world can inuence the environmental
behavior of organic chemicals.
Benzoic acid derivatives, which are considered as important
priority contaminants or typical environmental pollutants, may
impact on the environment in a number of ways and with great

Corresponding author. Tel.: +86 22 60601461.

E-mail address: jiaqingzhu88@126.com (J. Qing-Zhu).
potential risk to human health [5,6]. They are widely used reac-
tion intermediates and may be discharged into the environment
[7,8] as well as are often formed as a result of degradation of
aromatic compounds. For example, chlorinated benzoic acids
are the most common metabolites following the degradation of
poly-chlorinated biphenyls [9]. In order to evaluate the environ-
mental contamination performance of benzoic acid derivatives
in soil and groundwater, basic physicalchemical parameters
must be known.
The purpose of this work is to report solubilities of benzoic
acid derivatives in water at several temperatures and to test the
capability of selected equilibriummodels to describe these data.
We have chosen the Wilson [10] and H models [11,12] to pro-
duce rapid and easy methods to provide acceptable values of
solubility as a function of temperature.
2. Experimental
2.1. Materials
The benzoic acid derivatives tested include: benzoic acid
(>99%), o-nitro-benzoic acid (>99%), p-hydro-benzoic acid
(>99%), p-methyl-benzoic acid (>99%) and m-methyl-benzoic
0378-3812/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2006.10.014
166 J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172
Table 1
The meltingtemperatures (T
m
) andthe enthalpies of fusion(
m
H) of the benzoic
acid and its derivatives
Compounds T
m
(

C)
m
H (kJ mol
1
)
Benzoic acid 122.35 18.02
o-Nitro-benzoic acid 145.80 27.99
p-Hydrogen-benzoic acid 215.55 30.90
p-Methyl-benzoic acid 183.55 28.40
m-Methyl-benzoic acid 109.85 15.73
acid (>99%). The melting temperatures (T
m
) and the enthalpies
of fusion (
m
H) of the benzoic acid derivatives [13] are listed
in Table 1. These compounds were purchased from commer-
cial sources, and used without any further purication. Doubly
distilled water was used.
2.2. Apparatus and procedure
The apparatus, shown in Fig. 1, has been described in detail
previously [14], so only a brief presentation is made here. The
main elements are an equilibrium vessel, an electromagnetic
stirrer, a thermostatic controller, water bath, andlaser monitoring
equipment.
The experimental procedure measured the temperature of
dissolution of a known, xed-concentration solution contained
within a well-stirred vessel. In the procedure, heating is at a slow
rate with thorough mixing, so the measured benzoic acid deriva-
tive concentration is the equilibrium solubility at the measured
dissolution temperature.
Pre-weighed amounts of benzoic acid derivatives and water
were placed into a vessel. The vessel was then stoppered, con-
nected to a circulating water bath, and stirring was started. The
mixture was initially equilibrated at a temperature signicantly
below the dissolution temperature for at least 1 h. The tempera-
ture of the mixture was then slowly increased in stepwise fashion
until the temperature at which all the benzoic acid derivatives
had dissolved was reached. Near the dissolution temperature
Fig. 1. Equipment for measurement of solubility of benzoic acid derivatives
in water. 1: thermometer; 2: thermometer; 3: whisk machine; 4: thermostatic
controller; 5: electromagnetic stirrer; 6: whisk rotor; 7: equilibrium vessel; 8:
water bath; 9: laser; 10: laser receiver; 11: recorder.
Fig. 2. Experimental solubility of benzoic acid in water compared with literarual
data.
(more than 1

C below) the temperature increase was typically

kept at 0.2

C/20 min or slower.

The required temperature was maintained by circulating
thermostatically controlled water through the jacket. The laser
monitoring equipment was used to observe and monitor the dis-
solution condition of the solution. A steady laser beam passes
through an aperture and adjustable lens and then through the
solventsolute mixture. If there are solids in the path of the
beam, it will be scattered and the transmitted intensity will be
reduced. The intensity of transmitted laser is recorded by a com-
puter in terms of photovoltage. The corresponding temperature
at given composition is determined as the one at which the solid
phase just disappears.
During the experimental procedure, errors in the nal results
may arise in three ways: impurity of the compounds, weighing
error and temperature error. The weighing error can be neglected
by mass preparation using an analytical balance with an accu-
racy of 0.00001 g. The purity of the chemicals tested is >99%
and impurity appears to be a homolog that does not affect the
solubility data signicantly. The temperature error is greatest
uncertainty in the nal results. Therefore, the thermometer that
was used in the experiments was calibrated with an accuracy of
0.05

C and the rate of temperature increase was controlled

strictly at less than 0.2

C/20 min or even slower near the disso-

lution temperature.
The experimental setup and its accuracy were validated by
comparing the experimental solubility data of benzoic acid in
water withthose inliterature [15]. As showninFig. 2, the solubil-
ities obtained in this work are in good agreement with literature.
The deviation of the measured solubilities from literature val-
ues was <1%. In this work, the solubilities determined had an
average relative deviation (AAD) of <5%.
3. Results and discussion
3.1. Experimental results
Solubilities of benzoic acid derivatives in water were mea-
sured and are listed in Tables 25, where T is the temperature
J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172 167
Table 2
The solubility data of o-nitro-benzoic acid and regression results with Wilson equation and H equation
T (

C) x
exp
10
4
Wilson equation, (x
exp
x
cal
) 100/x
exp
H equation, (x
exp
x
cal
) 100/x
exp
ln
1
H
E
(J mol
1
)
19.12 5.560 15.3 2.2 4.20 1468.500
20.32 5.861 14.6 0.8 4.19 1547.999
21.43 6.131 13.7 0.0 4.18 1619.311
23.89 6.831 12.3 2.7 4.15 1804.194
24.36 6.812 10.1 1.0 4.15 1799.176
25.13 7.290 12.6 5.2 4.14 1925.425
28.34 7.70 3.5 0.5 4.11 2033.714
29.32 7.80 0.2 2.5 4.10 2060.125
29.84 7.98 0.0 0.5 4.10 2107.667
30.85 8.39 0.1 1.2 4.08 2215.955
31.92 8.910 1.0 3.8 4.07 2353.297
34.33 9.491 4.0 2.7 4.05 2506.75
35.43 9.642 7.5 0.9 4.04 2546.632
36.39 9.721 11.4 1.2 4.03 2567.497
37.42 10.454 8.7 2.8 4.02 2761.096
38.42 10.473 13.4 0.0 4.01 2766.115
39.53 10.79 15.7 0.3 4.00 2849.84
40.39 11.12 16.7 0.0 3.99 2936.999
41.28 11.34 19.0 0.7 3.98 2995.105
The x
exp
stands for the experimental solubility (in mole fractions of the solute). The x
cal
stands for the calculated solubility. The ln
1
is the logarithm innite
dilution activity coefcients. The H
E
indicates the molar mixing enthalpy of solution.
Table 3
The solubility data of p-hydro-benzoic acid and regression results with Wilson equation and H equation
T (

C)
exp
10
4
Wilson equation, (
exp

cal
) 100/
exp
H equation, (
exp

cal
) 100/
exp
ln
1
H
E
(J mol
1
)
18.92 4.561 3.9 0.0 2.62 644.8223
20.32 5.012 6.3 2.8 2.61 708.5835
25.62 5.931 2.0 4.4 2.58 838.5093
27.47 6.430 2.6 4.6 2.57 909.0566
30.17 7.310 2.3 3.6 2.56 1033.469
31.03 7.554 2.9 4.1 2.55 1067.965
31.82 7.992 0.8 1.8 2.55 1129.888
32.33 8.331 0.9 0.0 2.54 1177.815
33.19 9.184 6.5 5.9 2.54 1298.41
34.13 9.542 6.2 5.7 2.54 1349.023
35.62 9.944 3.8 3.5 2.53 1405.857
36.92 10.13 0.0 0.0 2.53 1432.153
37.85 10.54 0.0 0.0 2.52 1490.118
38.74 10.93 0.2 0.0 2.51 1545.255
39.19 11.22 0.4 0.6 2.51 1586.254
40.23 11.48 1.3 1.4 2.51 1623.012
Table 4
The solubility data of p-methyl-benzoic acid and regression results with Wilson equation and H equation
T (

C) x
exp
10
5
Wilson equation, (x
exp
x
cal
) 100/x
exp
H equation, (x
exp
x
cal
) 100/x
exp
ln
1
H
E
(J mol
1
)
30.85 4.548 9.0 4.7 6.35 297.8208
31.95 4.759 7.6 3.7 6.33 311.6379
33.15 4.865 3.6 0 6.31 318.5792
35.00 5.050 2.8 5.8 6.28 330.6937
36.00 5.275 3.8 6.4 6.26 345.4276
36.70 5.513 3.1 5.4 6.25 361.0127
37.20 5.843 0.0 1.9 6.24 382.6224
41.70 8.275 0.0 10.6 6.17 541.8792
44.70 9.068 10.3 6.0 6.12 593.808
47.20 9.743 4.6 1.8 6.08 638.0096
50.10 10.10 0.5 8.1 6.03 661.3874
168 J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172
Table 5
The solubility data of m-methyl-benzoic acid and regression results with Wilson equation and H equation
T (

C) x
exp
10
5
Wilson equation, (
exp

cal
) 100/
exp
H equation, (
exp

cal
) 100/
exp
ln
1
H
E
(J mol
1
)
23.80 2.961 3.3 6.7 9.58 74.00477
25.30 3.199 5.2 1.7 9.53 79.95139
27.40 4.217 0.0 4.7 9.46 105.3894
28.40 4.468 1.0 0.4 9.43 111.6662
29.10 4.997 1.1 4.3 9.41 124.8805
30.30 5.394 0.2 0.0 9.37 134.7911
31.00 5.724 0.1 1.2 9.35 143.0499
32.30 6.544 0.8 0.8 9.31 163.5315
32.90 7.112 1.7 1.6 9.29 177.7362
33.65 7.297 0.3 3.3 9.27 182.361
35.15 8.249 0.3 5.9 9.22 206.1452
36.05 9.002 0.2 5.4 9.20 224.9741
36.45 9.914 1.1 0.0 9.19 247.7666
36.55 10.443 2.1 4.1 9.18 260.9794
37.25 11.567 2.7 7.4 9.16 289.0562
38.45 11.805 0.0 1.8 9.13 295.0018
40.52 14.514 0.8 0.7 9.07 362.7136
42.02 17.224 1.4 2.2 9.02 430.4217
43.85 20.105 3.2 1.0 8.97 502.4194
(

C), and x
exp
stands for the experimental solubility (in mole
fractions of the solute). The experiments show that the sol-
ubilities of these compounds increase with temperature. The
components are sparingly soluble in water (<0.01 mol/L),
with solubilities that are very low, typically of the order of
10
4
10
5
mol/mol.
The solubilities from different researchers are compared
in Figs. 35. Benzoic acid has been studied several times in
the literature [15,16]. The solubilities of nitro-benzoic acid,
p-hydro-benzoic acid and p-methyl-benzoic acid in water as
a function of temperature T or at a few temperatures were
determined by Apelblat and Manzurola [15,17,18] and Li et
al. [19]. The solubilities in water as a function of temperature
T of o-nitro-benzoic acid and m-methyl-benzoic acid have
not been published before. As can be seen in Figs. 35, the
solubility data of this work and the measurements published
in literature are in reasonably good agreement, in particularly
Fig. 3. Experimental solubility of p-hydro-benzoic acid in water compared with
literatural data.
Fig. 4. Experimental solubility of o-nitro-benzoic acid in water compared with
literarual data.
for p-methyl-benzoic acid. To some extent, the differences
between this work and the work of Apelblat and Manzurola can
be caused by the different experimental approach. In case of
low solubilities, in particular, the extremely low solubilities of
Fig. 5. Experimental solubility of p-methyl-benzoic acid in water compared
with literatural data.
J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172 169
benzoic acid derivatives, analysis and especially the separation
of the solid dispersed in the liquid phase are difcult and
sensitive to deviations. As a consequence, slight deviations
between different solubility experiments can be considered
acceptable.
3.2. Models for solubility calculations
In general, solidliquid equilibria (SLE) can be described by
an equation containing pure solute properties such as enthalpy
of fusion, melting temperature and so on. If, as is the case in this
work, a solidsolid transition does not occur, the equation for
description of SLE can be simplied to the form shown as Eq.
(1):
ln
i
x
i
=

m
H
i
R

1
T

1
T
mi

(1)
where
m
H
i
is the enthalpy of fusion of the solute i, T
mi
the
melting temperature, T the absolute temperature, R the universal
gas constant, x
i
indicates the real mole fraction and
i
stands for
the activity coefcient. Eq. (1) was used with the experimental
data to determine parameters in an activity coefcient model by
regression.
According to Eq. (1), the activity coefcient
i
is a key value
in calculating the solubility, knowing T
mi
and
m
H
i.
. Out of
several activity coefcient models which can be selected, in this
work, the Wilson equation was chosen.
3.2.1. Empirical formula
Since the aqueous solubility is the highest equilibrium con-
centration of a compound in water at certain temperature, the
specied temperature is the most important and fundamental
parameter. In this work, an empirical formula shown in Eq. (2)
was used to correlate the aqueous solubilities of benzoic acid
derivatives, both the presented and literature results for ben-
zoic acid. All regressions produced high correlation coefcients
(R
2
>0.99), indicating satisfying descriptive capability of the
models obtained.
x = AT
3
+BT
2
+CT +D (2)
where x is the aqueous solubility (as mole fraction of the solute)
and T stands for the dissolving temperature (

C).
3.2.2. Wilson equation
For a binary system, the Wilson equation is equated as fol-
lows:
ln
1
= 1 ln (
2

12
+
1
)

1
+
2

12
+

2

21

2
+
1

21

(3)
of which
ij
is the Wilson equation parameter, which is a func-
tion of temperature.

ij
=
V
j
V
i
exp

g
ji
g
ii
RT

(4)
In general, the energy parameter (g
ji
g
ii
) in the Wilson
equation is thought to be independent of temperature. There-
fore, if the difference in molar volume between the constituents
is ignored, two parameters remain in the Wilson equation for a
binary system: (g
21
g
11
) and (g
12
g
22
).
Eq. (1) was combined with the Wilson equation to determine
the Wilson parameters by regression of the measured aqueous
solubilities. The results are shown in Tables 25. The values
of the objective function AAD and the parameters that were
determined by regression are listed in Table 6.
To test the accuracy of the regressed parameters of the Wilson
equation, the degree of condence was calculated according to
the F-function, the degree of condence is calculated with the
incomplete beta function. The results show that all the degrees
of condence of the Wilson parameters (g
21
g
11
) regressed for
the different substances are >0.9825. For the Wilson parameters
(g
12
g
22
), the degree of condence is >0.9985.
3.2.3. H equation
The H equation, Eq. (5), is another way to describe the
solution behavior and was suggested rstly by Buchowski et al.
[11,12], which is used particularly for SLE. It is thermodynam-
ically correct and gives a good description of experimental data
for many systems although only two parameters, and H, are
involved.
ln

1 +
(1 x
i
)
x
i

= H

1
T

1
T
mi

(5)
In Eq. (5), and Hare two equation parameters, and x
i
stands
for the mole fraction of a solute in a binary, saturated solution.
For all the systems studied, the parameters and H, which were
regressed using a non-linear optimization method, showed no
Table 6
The regression results of Wilson equation and H equation
Samples Wilson equation H equation
g
21
g
11
g
12
g
22
AAD
*
H (K) AAD
*
o-Nitro-benzoic acid 7788.55 40298.17 9.5 0.008207 321046 1.5
p-Hydrogen-benzoic acid 3925.87 23547.88 2.5 0.02243 173764 2.4
p-Methyl-benzoic acid 13526.84 28336.41 5.1 0.005584 791050 4.9
m-Methyl-benzoic acid 23625.47 113.859 1.9 0.03064 302472 2.7
AAD

n
|XexpX
cal
|
Xexp

100
n
.
170 J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172
Table 7
The solubility data of benzoic acid, the ln
1
and the H
E
T (

C) x
exp
10
4
ln
1
H
E
(J mol
1
)
17.20 3.889 5.78 2114.508
18.15 4.011 5.77 2179.737
19.86 4.272 5.74 2321.066
22.82 4.623 5.69 2511.318
24.00 4.951 5.67 2690.698
24.23 4.972 5.67 2701.569
30.01 5.948 5.58 3234.273
31.33 5.988 5.56 3256.016
33.57 6.801 5.53 3696.312
35.29 7.071 5.50 3843.077
40.01 8.285 5.43 4500.803
40.03 8.354 5.43 4538.854
41.50 8.752 5.41 4756.284
signicant variation with temperature. The regression results of
the aqueous solubilities and the values of the parameters and
H as well as AAD for the solubility calculations are shown in
Tables 26.
3.3. Comparison among the solubility of substances
For completeness of discussion and in order to calculate
the innite dilution activity coefcients (ln
1
) and the par-
tial molar excess enthalpy of solution (H
E
), previously reported
solubilities of m-nitro-benzoic acid [11] were also included in
the analysis of this work.
Since the solubilities of the benzoic acid derivatives in water
are very low, the correlations (3) and (5) can be extrapolated to
the limit of innite dilution in the solutes. The innite dilution
activity coefcients (ln
1
), calculated with Wilson equation,
are shown in Tables 25, 7 and 8. It becomes clear that the ln
1
of p-hydro-benzoic acid are much lower than those of the other
components studied. This can be attributed to the smaller size
of the p-hydro-benzoic acid molecules and stronger interactions
of the p-hydro-benzoic acid molecules with water. According
Table 8
The solubility data of m-nitro-benzoic acid, the ln
1
and the H
E
T (

C) x
exp
10
4
ln
1
H
E
(J mol
1
)
26.05 2.090 5.61 187.1304
27.45 2.350 5.59 210.4098
29.60 2.880 5.55 257.8639
31.20 2.890 5.52 258.7592
33.22 2.871 5.49 257.0581
35.50 3.527 5.45 315.7937
37.54 4.256 5.42 381.0655
38.82 4.544 5.40 406.8519
39.80 4.954 5.38 443.5617
41.00 5.081 5.36 454.9328
41.81 5.856 5.35 524.3232
42.78 6.084 5.33 544.7374
43.24 6.292 5.32 563.3609
44.13 6.501 5.31 582.0740
45.70 7.787 5.28 697.2174
47.45 8.583 5.25 768.4881
Fig. 6. The relationship between ln r and 1/T.
to the analysis of Tsonopoulos and Prausnitz [20] for methyl-
benzoic acid, its molecules are bigger, while its interactions with
water are expected to be weaker and its activity coefcients are
therefore higher than those of others.
The innite dilution activity coefcients (ln
1
) versus 1/T
are plotted in Fig. 6. According to Eq. (6), tting to Eq. (7) yields
the parameter B, which is equal to R times the partial molar
excess enthalpy at innite dilution, and A which is the partial
molar excess entropy at innite dilution compared to the solute
as a hypothetical liquid. Positive values of A and B, shown in
Table 9, indicate that both enthalpic and entropic effects reduce
the solubility. This is the case for most of the compounds in
Table 9. Note that the m-methyl substitution has a much lower
value of A and a higher value of B than the others, exceed-
ing
m
H. This is an indication of the hydrophobic nature of
the methyl substitution and the hydrophilic nature of the other
substitutions.

ln
i
T

p,x
=

H
E
i
RT
2
(6)
ln r
1
= A +B
1
T
(7)
Due to the different positions of NO
2
group in the benzene
ring, the molecular volume of the m-nitro-benzoic acid is larger
than that of the o-nitro-benzoic acid. Thus, much more energy
would be needed to break the hydrogen bonds of water in the
m-nitro-benzoic acid solution. As a consequence, the value B of
m-nitro-benzoic acid is larger than that of o-nitro-benzoic acid.
Table 9
The tting results of ln
1
and 1/T
Samples A B R
2
Benzoic acid 1 1388.8 1
o-Nitro-benzoic acid 1 936.8 1
p-Hydrogen-benzoic acid 0.9991 472.45 1
p-Methyl-benzoic acid 0.9998 1627.1 1
m-Methyl-benzoic acid 0.0021 2843.3 1
m-Nitro-benzoic acid 0.293 1591.8 1
J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172 171
On the other hand, though both OH group and CH
3
group are
on the p-position in the benzene ring, because rstly, the OH
is polar and the CH
3
is non-polar, and secondly, the OH is
similar to that of water, much more hydrogen bonds with water
molecules would be formed in the p-hydro-benzoic acid solu-
tion. As a result, the value of B of p-hydro-benzoic acid solution
is much lower than that of p-methyl-benzoic acid solution, as
indicated in Table 9. Hence, it could be concluded that the struc-
tural andinteractionorigins might affect the dissolutionbehavior
markedly.
In the H equation, the parameter H is related to the enthalpy
of solution per mole of solute. The expression due to Buchowski
et al. [11] is given in Eq. (8), where H
E
is the molar mix-
ing enthalpy of the solution. Eq. (8) can be used to estimate
the values of H
E
in order to get a better understanding of the
solution characteristics. The values of H
E
are also shown in
Tables 25, 7 and 8:
HR =
m
H
i
+
H
E
x
i
(8)
The values of H
E
are positive, whichindicates the existence of
repulsive interaction between benzoic acid derivates and water
molecules. Also, if there are two polar groups in the benzene
ring, like in nitro-benzoic acid and in hydro-benzoic acid, the
values of H
E
are much higher than those with only one polar
group in the benzene ring.
3.4. Comparison between models
From the results shown in Tables 26, it can be observed that
the goodness of t for the Wilson equation and the H equation
are almost the same for p-hydro-benzoic acid and p-methyl-
benzoic acid. In the case of o-nitro-benzoic acid, the Hequation
is much better than the Wilson equation, which is in correspon-
dence with the results by U.J. Domanska and Mapeisheng et al.
[21,22,23]. Also, it seems that the problemwith the Wilson equa-
tion for the o-nitro compound is that its parameter is temperature
dependent. This is not surprising since this substance would have
internal H-bonding that would decrease more rapidly with tem-
perature than the physical effects. This will be investigated in
future work.
4. Conclusions
Determination of the temperature dependence of solubili-
ties in water is important for improvement of the predictive
capability of environmental models. Using a laser monitoring
observation technique, solubilities of benzoic acid derivatives
in water as a function of temperature have been determined
in this work. From all results, some conclusions can be
drawn:
1. The solubilities of o-nitro-benzoic acid, p-hydro-benzoic
acid, p-methyl-benzoic acid and m-methyl-benzoic acid in
water are very low, usually of the order of 10
4
10
5
mol/
mol.
2. The solubilities of the compounds increase with temperature.
Owing to the special molecular structure, the solubilities of
different benzoic acid derivatives in water as a function of
temperature vary signicantly.
3. Empirical formulas are applicable to regress the aqueous sol-
ubility of these compounds, and the relativity coefcients R
2
were above 0.99.
4. The experimental solubilities are well represented by the
Wilson equation and especially the H equation.
List of symbols
A parameter in Eq. (7)
B parameter in Eq. (7)
g
21
g
11
, g
12
g
22
parameters in Wilson equation
H parameters in H equation (K)
H
E
molar mixing enthalpy of solution

H
E
i
partial molar excess enthalpy of solution
ln
1
innite dilution activity coefcient in the solutes
R Gas constant, 8.314 J mol
1
K
1
T experimental temperature in Eq. (1) (K)
T
mi
fusion temperature in Eq. (1) (K)
x
1
mole fraction of the solute in Wilson equation
x
2
mole fraction of the solvent in Wilson equation
Greek letters

ij
parameters in Wilson equation
Acknowledgement
Thanks for the fund support of the Nation Natural Science
(No. 20676101).
References
[1] L. Xu, Y.P. Wu, C.Y. Hu, et al., Sci. China (Ser. B) 30 (2000) 17.
[2] L.-S. Wang, S.-K. Han, Progress in Organic Pollution Chemistry [M],
Chemical Industry Press, Beijing, 1998, p. 181.
[3] L.-S. Wang, Y.-H. Zhao, H. Gao, Environ. Chem. 11 (1992) 6469.
[4] F. Antonio, D.G. Antonio, Chemosphere 45 (2001) 10631070.
[5] D.J.W. Blum, R.E. Wand Speece, Environ. Sci. Technol. 24 (1990)
284293.
[6] Y.H. Zhao, G.D. Jia, M.T.D. Croninb, U.J.C. Deardenb, Sci. Total Environ.
216 (1998) 205215.
[7] Y.-H. Zhao, X. Yuan, L.-H. Yang, L.-S. Wang, Bull. Environ. Contam.
Toxicol. 57 (1996) 242249.
[8] M.E. Ramos-Nino, M.N. Clifford, M.R. Adams, J. Appl. Bacteriol. 80
(1996) 303310.
[9] A.C. Layton, C.A. Lajoie, J.P. Easter, M.J. Beck, G.S. Sayler, Ann. N.Y.
Acad. Sci. 721 (1994) 407421.
[10] Han, S.-J. (translation), Phase Equilibria in Chemical Engineering [M],
Petro-Chemical Industry Press, Beijing, 1991.
[11] H. Buchowski, A. Ksiazcak, K.S. Pietrzy, J. Phys. Chem. 84 (1980)
975979.
[12] H. Buchowski, Fluid Phase Equilib. 25 (1986) 273278.
[13] Landolf-Bornsfein Numerical Data and Functional Relationships in Sci-
ence and Technology, New Series Group, vol. 8, sub-volume A, Enthalpies
of Fusion and Transition of Organic Compounds, 1995.
[14] Q.-Z. Jia, P.-S. Ma, C. Wang, Q. Wang, Environ. Chem. 25 (2006) 128
132.
[15] H. Stephen, T. Stephen, Solubilities of Inorganic and Organic Compounds,
Oxford Pergamon, London, 1969.
172 J. Qing-Zhu et al. / Fluid Phase Equilibria 250 (2006) 165172
[16] A. Apelblat, E. Manzurola, J. Chem. Thermodyn. 38 (2006) 565571.
[17] E. Manzurola, A. Apelblat, J. Chem. Thermodyn. 34 (2002) 1127
1136.
[18] A. Apelblat, J. Chem. Thermodyn. 29 (1997) 15271533.
[19] D.-Q. Li, D.-Z.H. Liu, F.-A.N. Wang, J. Chem. Industry Eng. (China) 52
(2001) 541544.
[20] C. Tsonopoulos, J.M. Prausnitz, Ind. Eng. Chem. Fundam. 10 (1971)
593600.
[21] U.J. Domanska, Fluid Phase Equilib. 26 (1986) 201220.
[22] P.Sh. Ma, M.M. Chen, Chin. J. Chem. Eng. 11 (2003) 334337.
[23] P.Sh. Ma, M. Chen, M.Y. Dong, Chin. J. Chem. Eng. 10 (2002) 323
327.