Fluid Phase Equilibria 297 (2010) 113120

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Fluid Phase Equilibria
j our nal homepage: www. el sevi er . com/ l ocat e/ f l ui d
Solubility of benzoic acid in acetone, 2-propanol, acetic acid and cyclohexane:
Experimental measurement and thermodynamic modeling
Bingwen Long

, Jing Li, Rongrong Zhang, Li Wan

College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
a r t i c l e i n f o
Article history:
Received 11 February 2010
Received in revised form 5 May 2010
Accepted 26 June 2010
Keywords:
Benzoic acid
Solubility
Gravimetric method
Modeling
Predicting
a b s t r a c t
In this study the solubility of benzoic acid in acetone, 2-propanol, acetic acid and cyclohexane was exper-
imentally determined over the temperature range of (277346) K at around 5K intervals by employing
a gravimetric method. The experimental results showed that acetone had the best solubility for ben-
zoic acid followed by 2-propanol, acetic acid and cyclohexane and the solubility in acetic acid had the
strongest positive temperature dependency. The newly measured solubility data was also compared
with the available literature data. Several commonly used thermodynamic models, including the empir-
ical Vant Hoff equation, the zh equation, the Wilson, NRTL and UNIQUAC equations, were applied to
correlate the experimental solubility data. The adjustable parameters for each model were optimized by
tting the solubility data measured in this work. It was found that the three-parameter NRTL equation
could give the best correlation results. Better predictions of the solubility of benzoic acid in acetic acid
at higher temperature were observed using the Wilson and UNIQUAC equations than the other three
equations which all gave underestimations.
2010 Elsevier B.V. All rights reserved.
1. Introduction
The knowledge of the phase equilibriumthermodynamics plays
a very important role in the design, analysis and optimization of
the separation and purication processes in many industrials like
chemical, petrochemical, food, pharmaceutical and material [1].
For most solid products, solution crystallization is one of the most
commonlyemployedoperations for their recoveryandpurication,
where the accurate quantity information of the solute solubility on
solvents and temperature is essential. With the detailed solubility
data, optimal crystallizer congurations and operation conditions
together with the selection of the solvent for a specic solute can
be achieved [2,3]. Because of the widely recognized importance of
solubility data in science and industry, vast amounts of quantita-
tive measurements of solubility have been made. In addition, many
efforts have been put forth to develop appropriate thermodynamic
models to correlate and predict the solubility phenomena, which
could offer us more understandings of the interactions between
the solute and the solvents [4]. With the fast growth of computa-
tional power, thermodynamic predictive methods have gained an
greatly increasing attention, especially when the experimental sol-
ubility data is not readily available. Experimental work, however,
still remains the best method to obtain reliable solubility data.

Corresponding author. Tel.: +86 10 64423603; fax: +86 10 64434773.

E-mail address: bingwen long@163.com (B. Long).
Benzoic acid (C
7
H
6
O
2
, CAS Registry No. 65-85-0) is a colorless
crystalline solid, which is widely used as an important interme-
diate for preparation of many other organic substances applied in
the elds of pharmaceuticals, resins, plasticizers, dyes, cosmetics
and preservatives [5]. Benzoic acid is the simplest aromatic car-
boxylic acid that can be produced in large quantities and with high
purity. Solution crystallization is often used as the nal purica-
tion step in its production. A lot of research has been conducted
to understand the solubility of benzoic acid in different solvents
such as water, alcohols, acids, alkanes, and aromatics, and some
of the data can be found in several solubility data compilations
[68] and journal articles [916]. In this work, the solubility of ben-
zoic acid in four different categories of organic solvents of acetone,
2-propanol, acetic acid and cyclohexane was investigated. These
solvents may have potential industrial applications for the puri-
cationof benzoic acid. Preliminaryliterature searchof the solubility
data for these solvents showed either signicant conicting results
(in case of acetic acid, acetone and cyclohexane) or the data avail-
able only at limited temperature (in case of acetone, 2-propanol
and cyclohexane). In addition, some data were reported with little
or no descriptionof the experiments, whichmakes the assessments
problematic. Therefore, the main purpose of this work is to obtain
new experimental solubility data of benzoic acid in these solvents,
compare them with the published ones available and evaluate dif-
ferent thermodynamic models by employing themto correlate and
predict the experimental solubility data. To do this, the solubil-
ity of benzoic acid in the four solvents is systematically measured
0378-3812/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2010.06.021
114 B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120
Table 1
Comparison of measured densities and refractive indices nD of the pure components with literature values at 293.15K.
Solvent Purity (%) (gcm
3
) nD
This work Literature This work Literature
Acetone >99.5 0.8048 0.8054 1.3591 1.3588
2-Propanol >99.7 0.7849 0.7855 1.3780 1.3776
Acetic acid >99.5 1.0474 1.0490 1.3726 1.3720
Cyclohexane >99.5 0.7779 0.7786 1.4247 1.4255
in a temperature range of (277346) K at around 5K increments.
Following this, a detailed comparison has been made with the liter-
ature data. Meanwhile, different thermodynamic models including
empirical Vant Hoff equation, the zh equation, the Wilson, NRTL
and UNIQUAC equations are investigated for the correlation and
prediction of the solubility of benzoic acid.
2. Experimental
2.1. Materials
Analytical benzoic acid was purchased from Shantou Xilong
Chemical Co. with stated purity of >99.5% by mass. The melting
point range of benzoic acid samples was determined with a dig-
ital melting point system (type WRS-1A1B, HangZhou Kebo Co.)
as between 394.75K and 395.70K and a value of 395.52K was
found in the handbook [17]. All the solvents used were of ana-
lytical grade and purchased from Beijing Chemical Reagent Co.
with at least stated purity of 99.5%. Densities and refractive indices
of the solvents at 293.15K were measured and the results are
listed in Table 1 together with literature data [17] for comparison.
Densities were measured using 5cm
3
pycnometers and refractive
indices were measured with a Abbe-3L refractometer (type WYA-
2W, Shanghai Optical Instrument Co.). The devices were carefully
pre-calibrated and temperature controlled. All the chemicals were
used as received.
2.2. Procedure and equipment
The solubilityof benzoic acidindifferent solvents was measured
using the static analytical method and the compositions of the sat-
urated solutions were determined using the gravimetric method.
The apparatus anddetailedprocedure of the solubility experiments
have already beendescribedinour previous work [1822] andhere
only some apparatus changes are described. During each solubil-
ity measurement, an excessive amount of solutes were put into
a double layer jacket glass equilibrium cell, which had a work-
ing volume of 200mL. The temperature of the equilibriumcell was
controlled by circulating water from a thermostat (type DTY-15A,
Beijing DeTianYou Co.) through the jacket of the cell. The solution
equilibrium temperature was measured using a glass thermome-
ter with 0.05K uncertainty. Continuous stirring was adopted for
fully mixing the suspension using a magnetic stirrer. The stirring
was kept for at least 3h and then the solution was kept still for
1h in order to allow the undissolved solids to settle down in the
lower portion of the equilibrium cell. Different dissolution times
were tested and it was found that 3h was sufcient for benzoic
acid to reach equilibrium in all the solvents. After enough time
of solidliquid mixing and gravitational settling, around 23mL
clear solution was quickly taken out to another previously weighed
measuring vial by a suitably pre-warmed syringe with a long tip
protected by a micro screen. The vial was then quickly and tightly
closed and weighed again to determine the mass of the sample.
Then the vial was put into a drying oven (type STED-01, Wujiang
Shentai Oven Instrument Co.) with the cap half-closed to allowthe
complete evaporation of the solvent. The temperature of the oven
was well controlled and the vial was covered with a piece of stain-
less steel lter cloth (74m) to prevent dust contamination. After
at least 12h, the vial was taken out and placed in a desiccator with
silica gel for another 2h in order to reach the ambient tempera-
ture. After that, the vial together with the solutes remaining was
weighed again. Periodical measurements were conducted until the
constant weight of the vial was obtained. An analytical balance
(type Adventurer AR2140, OHAUS Co.) with precision of 0.0001g
was used for all the mass measurements. Then the solubility was
calculated accordingly. An average value was taken from at least
three independent measurements for each temperature. The sol-
ubility data was measured at around 5K increments from 277K
to 346K. The estimated uncertainty of the solubility values based
on the error analysis and repeated observations was within 1% for
acetone, 2-propanol and acetic acid, and 2.5% for cyclohexane.
3. Results and discussion
3.1. Solubility data
The measured solubility data of benzoic acid in acetone, 2-
propanol, acetic acid and cyclohexane at different temperature is
listed in Table 2. For better understanding and comparison, the sol-
ubility data in the table is rstly reported on a xed solvent mass
basis as molality, m (mol kg
1
), which is dened as the amount of
the solutes dissolved in 1kg solvent at saturation. The molality sol-
ubility of benzoic acid in different solvents is compared and shown
in Fig. 1. As can be seen from the gure, acetone exhibits the high-
est solubility for benzoic acid but very close to 2-propanol. At most
temperatures, thesolubilityorder inthesesolvents was determined
as acetone >2-propanol >acetic acid>cyclohexane. This solubility
order follows the rule of Like dissolves like and can reasonably be
related to the possibility to form hydrogen bond between the ben-
zoic acid molecules and the solvent molecules. One among them,
cyclohexane is a typical non-polar solvent and its saturated and
stable molecular structure determines that it essentially has no
Fig. 1. Molality solubility of benzoic acid in different solvents: ( ) Acetone; ( )
2-propanol; () Acetic acid; ( ) Cyclohexane.
B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120 115
Table 2
Experimental solubility (molality mand molar fraction x) of benzoic acid in different
solvents.
Solvent T (K) m (mol kg
1
) x
Acetone 277.59 2.498 0.1267
282.21 2.874 0.1430
287.03 3.221 0.1576
287.19 3.208 0.1571
293.20 3.659 0.1753
298.15 4.105 0.1925
302.95 4.606 0.2111
307.75 5.178 0.2312
313.05 5.834 0.2531
317.63 6.580 0.2765
322.72 7.496 0.3033
2-Propanol 278.06 2.455 0.1286
282.96 2.775 0.1429
288.15 3.158 0.1595
293.11 3.500 0.1738
297.79 3.960 0.1922
303.45 4.547 0.2146
308.09 5.031 0.2321
312.80 5.622 0.2525
317.85 6.409 0.2780
322.78 6.993 0.2959
328.20 8.015 0.3251
333.20 8.825 0.3465
338.15 9.921 0.3735
343.10 11.60 0.4107
Acetic acid 292.95 2.455 0.1285
298.45 2.895 0.1481
303.05 3.303 0.1655
307.75 3.847 0.1877
312.15 4.447 0.2107
318.35 5.163 0.2367
323.15 6.041 0.2662
327.95 7.025 0.2967
332.75 8.131 0.3281
337.15 9.111 0.3536
342.75 11.14 0.4008
346.65 12.31 0.4250
Cyclohexane 283.15 0.03790 0.003179
287.95 0.05639 0.004724
293.16 0.08874 0.007413
298.00 0.1316 0.01095
303.30 0.1844 0.01528
308.02 0.2490 0.02052
313.18 0.3704 0.03023
317.75 0.4566 0.03701
322.91 0.5831 0.04678
328.18 0.7124 0.05656
333.11 0.9294 0.07254
337.98 1.224 0.09341
342.80 1.656 0.1223
chance to form intermolecular hydrogen bonds with benzoic acid
molecules. Similar to benzoic acid, acetic acid has the group COOH,
which can be both the hydrogen bond acceptor (the carbonyl) and
the donor (the hydroxyl). Incase of 2-propanol, hydrogenbonds are
easily set up between its slightly positive hydrogen atoms and the
lone-pairs on oxygen atoms in benzoic acid molecules. Acetone has
a similar carbonchainstructure to2-propanol andthe oxygenatom
with negative charge makes it a nice hydrogen bonds acceptor for
the hydroxyl group in benzoic acid molecules.
As for the temperature effect, the solubility of benzoic acid in all
the solvents increases with the raise of temperature. The solubil-
ity in acetic acid shows the strongest dependency on temperature
while cyclohexane exhibits the least one. At higher temperature,
acetic acid will give a solubility for benzoic acid over 2-propanol as
Fig. 1 shows.
Comparisons have been made between the experimental solu-
bility data in this work and those already available in the literature.
Fig. 2. Comparison of the solubility of benzoic acid in acetone: () this work; ( )
Mortimer [23]; ( ) Beerbower et al. [9].
Fig. 2 shows the comparison of the solubility of benzoic acid in
acetone. It can be seen from the gure that there is a fairly good
agreement between the data from Mortimer [23] and those mea-
sured in this work, though at lower temperature our data seems a
litter lower. Mortimers workwas madealmost 90years agoandthe
experimental details were not mentionedinhis paper. Onthe other
hand, the solubilitydata at 298.15KreportedbyBeerbower et al. [9]
agrees with our results quite well in Fig. 2. In the case of acetic acid,
Wang et al. [15] recently reported their measured solubility data,
whichis considerablylower thanthat fromLiuet al. [14], MaandXia
[16] and Kendall [41]. The comparisons are shown in Fig. 3. As was
observed in that gure, our measurements in this work support the
Liu, Ma, and Kendalls results. Here it is worthwhile to mention that
Wang and us both employed the gravimetric method to measure
the solubility while Liu and Ma adopted the dynamic method and
Kendall usedthe freezing-point method. As for 2-propanol, the only
data available was fromBeerbower et al. [9] at 298.15K. Their mole
fraction solubility value (0.1937) is converted as 3.998mol kg
1
.
There is a good agreement since our experimental data at 297.79K
is 3.960mol kg
1
. Finally, the solubility of benzoic acid in cyclo-
hexane was examined. Ksiazczak [42] measured the solubility data
of benzoic acid in cyclohexane from 309.65K to 395.40K using
a synthetic method. The comparisons betweenour measurements
Fig. 3. Comparison of the solubility of benzoic acid in acetic acid: () this
work; ( ) Wang et al. [15]; ( ) Liu et al. [14]; ( ) Ma and Xia [16]; ( )
Kendall [41].
116 B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120
Fig. 4. Comparison of the solubility of benzoic acid in cyclohexane: () this work;
( ) Ksiazczak [42].
and his results are shown in Fig. 4. As was observed in Fig. 4,
our measurements is a litter higher than the solubility from Ksi-
azczak. In addition, at 298.15K, the value from Beerbower et al.
[9] is 0.0102 (mole fraction, 0.1224mol kg
1
) and that from Acree
and Bertrand [24] is 0.0115 (mole fraction, 0.1382mol kg
1
). A
much lager value of 0.560mol L
1
was reported by Dearden and
OSullivan et al. [25] but without experimental description, which
was calculated as 0.724mol kg
1
assuming the volume unit stood
for thesolvent. Our result of 0.1316(mol kg
1
) at 298Kconrms the
former two authors work. At 303.15K, the value from Acree and
Bertrand [24] is 0.0146 (mole fraction, 0.1760mol kg
1
) and that
fromHancock et al. [26] is 0.0143 (mole fraction, 0.1724mol kg
1
).
Our data of 0.1844mol kg
1
at 303.30Kis a littlehigher. Acree, Han-
cock and Beerbower all employed the static method to measure the
solubility. The equilibrium solution composition was determined
by titration, gravimetric method and spectrophotometric analysis,
respectively. The claimed uncertainties are less than 1%, 3%, and 3%,
respectively, while ours is 2.5%.
3.2. Thermodynamic modeling
For the thermodynamic modeling purpose, the molality sol-
ubility data was rst transformed into molar fraction x and the
calculated values are listed in Table 2. Only the data measured in
this work was used for the modeling work. Commonly, the tem-
perature dependence of the solubility of a solute in solvents can be
modeled in three ways, namely empirical correlation, non-activity
coefcient method and activity coefcient method.
A frequently used empirical equation is the so-called Vant Hoff
relation, which correlates the natural logarithm of molar fraction
solubility x against the reciprocal of the absolute temperature T
[27],
ln x = u +
b
1
+
c
1
2
(1)
in which a, b, and c are the empirical parameters, which could be
regressed from the experimental solubility data by multivariable
least-square method. The standard deviations o were determined
by:
o =

N
P
i=1
(x
cal
i
x
exp
i
)
2
N
P
(N
P
n)
(2)
where N
P
refers to the number of data points for each solvent and
n is the number of model parameters. The superscripts exp and cal
Fig. 5. Vant Hoff plot of molar fraction solubility of benzoic acid in different sol-
vents: ( ) acetone; ( ) 2-propanol; ( ) acetic acid; ( ) cyclohaxane; ()
calculated by Eq. (1).
stand for the experimental and calculated solubility, respectively.
Table 3presents the regressedvalues of the parameters inEq. (1) for
each solvent in combination with the standard deviation o and the
squaredcorrectioncoefcient of theregressionR
2
values. Thegood-
ness of the t of Eq. (1) to the experimental data can be expressed
by the average absolute percent deviation (AAPD). The AAPD was
calculated according to the following denition:

AAPD
=
1
N
P
N
P

i=1

x
cal
i
x
exp
i
x
exp
i

100% (3)
The calculated
AAPD
for each solvent is also presented in Table 3.
The solubility curves calculated by Eq. (1) are plotted in Fig. 5. It
can be seen from Table 3 and Fig. 5 that the experimental solu-
bility data was well reproduced by the Vant Hoff equation and
the calculated overall average
AAPD
is 1.15%. In addition, with the
regressed parameters, the apparent Vant Hoff enthalpy of solution
at saturation can be calculated straightforward as [27]:
^H
VH
sol
= R1
2
_
ln x
1
_
sat
= R
_
b +
2c
1
_
(4)
In Fig. 5, a decline in the slope of the Vant Hoff curve with an
increase of solubility is observed, which indicates a decrease in
the Vant Hoff enthalpy of solution. However, acetone shows an
exception to this trend because of its positive c value. Similar
result was observed in the measurements of the solubility of p-
hydroxybenzoic acid in acetone [27].
The zh equation, also known as BuchowskiKsiazczak equa-
tion, is a distinguished non-activity coefcient method, which
was originally proposed by Buchowski et al. [28] and practically
couldbe applicable tomost solidliquidequilibriumsystems giving
excellent correlation results with just two adjustable parameters
[19,21,29]. The zh equation is given as:
ln
_
1 +z
1 x
x
_
= zh
_
1
1

1
1
m
_
(5)
Transforming Eq. (5) for an explicit form of x yields:
x =
z
c
zh(1
1
1
1
m
)
1 +z
(6)
wherexis themolar fractionsolubilityat temperatureT; T
m
denotes
the melting point of the solute. z and h are two adjustable param-
eters to be determined from the solubility data. The parameter
B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120 117
Table 3
Regression results of Vant Hoff equation (Eq. (1)): parameter values (a, b and c), the average absolute percent deviation
AAD
, the squared correction coefcient of the
regression R
2
and standard deviation o.
Solvent a 10
3
b (K) 10
5
c
AAD
R
2
10
3
o
Acetone 6.0996 2.9256 1.8406 0.63 0.999979 0.45
2-Propanol 3.9085 1.6240 0.09250 0.54 0.999976 0.71
Acetic acid 4.8518 1.7218 0.8830 0.62 0.999975 0.69
Cyclohexane 8.5248 8.7661 22.59 2.75 0.999882 0.99
regression was performed by minimization of the following objec-
tive function using the LevenbergMarquardt method:
Minj
1
(z, h) =

N
P
_
x
cal
x
exp
x
exp
_
2
(7)
The regressed z, h parameters as well as the calculated absolute
average deviations
AAPD
and the standard deviations o for each
system are listed in Table 4. It can be seen from the table that
the zh equation with regressed parameters satisfactorily corre-
lates the solubility data for the four systems investigated with only
two parameters. The calculated overall average
AAPD
with the zh
equation for the four solvents is 2.67%.
In the zh model, the parameter z could be approximately
regardedas the meanassociationnumber of solute molecules inthe
solution and h was related to the excess mixing enthalpy of solu-
tionper mole of solute [19,28,30]. Thus fromthe zvalues inTable 4,
it indicates that there is no obvious association during the benzoic
acid dissolution in acetone, 2-propanol and acetic acid except for
cyclohexane, whose zvalue was determinedlarger than1. The self-
association of benzoic acid molecules in hydrocarbon solvent has
already been reported by several researchers from the partition
coefcient measurements of benzoic acid [21,31].
As derived by Buchowski et al. [28], the excess molar mixing
enthalpy H
E
(J mol
1
) at the saturation points could be estimated
from the obtained parameter h and the enthalpy of melting of the
solute ^H
m
as:
H
E
= (hR ^H
m
)x (8)
where ^H
m
is the melting enthalpy of the solute, (J mol
1
); R is the
gas constant, 8.314 (J mol
1
K
1
). The melting enthalpy of benzoic
acid was reported as 18,006 (J mol
1
) [17], so it is clear that positive
H
E
values at the saturation points for all the solvents investigated
will be obtained. As Li et al. [30] discussed, the positive H
E
val-
ues indicate that there are possible repulsive interactions between
benzoic acid molecules and the solvent molecules.
Another commonly used method to model the solubility of solid
solute in liquid solvent is to use the activity coefcient models, an
excess Gibbs energy based method. Starting from the solidliquid
equilibrium criteria, by setting up a virtual thermodynamic Hess
recycle, Prausnitz et al. [32] mathematically proved that the equi-
librium solubility of solute in liquid solvent can be modeled by the
following rigorous thermodynamics equation, where the solid is
assumed to be pure and that the triple point temperature of the
solute can be replaced by its melting temperature [32]:
ln x
2
= ln
2
+
^Hm
R
_
1
1m

1
1
_

1
R1
_
1
1m
^Cp d1 +
1
R
_
1
1m
^Cp
1
d1 (9)
Table 4
Regression results of zh equation: parameter values (z and h), the average absolute
percent deviation
AAD
and standard deviation o.
Solvent z h
AAD
10
3
o
Acetone 0.5668 2591.20 0.60 0.40
2-Propanol 0.4874 2774.66 1.17 1.16
Acetic acid 0.9169 2431.96 0.71 0.77
Cyclohexane 1.2713 4602.47 7.84 1.03
where subscript 2 denotes solute, while 1 denotes solvent; x is the
molar fraction solubility of the solute and is the activity coef-
cient in the solution at equilibrium; ^C
P
is the difference in molar
heat capacity between the melting and solid state of the solute,
(J mol
1
K
1
). The following physical property data for benzoic acid
was usedinthe calculations, ^H
m
=18,006 (J mol
1
), T
m
=395.52K,
^C
P
=57.86 (J mol
1
K
1
) [33].
To estimate the activity coefcient
2
, three commonly used
expressions for strongly non-ideal binary mixtures were chosen,
namely the Wilson, NRTL and UNIQUAC equations. The expressions
of the equations for binary systems are explained as below:
(1) Wilson equation. Based onthe local composition concept, Wil-
son [34] proposed a distinguished expression for excessive
Gibbs free energy and the accordingly derived liquid phase
activity coefcient of the solute is given by:
ln
2
= ln(x
2
+/
21
x
1
) +x
1
_
/
21
x
2
+/
21
x
1

/
12
/
12
x
2
+x
1
_
(10)
in which x
1
, x
2
are the molar fraction of the solvent and
solute, respectively. /
12
and /
21
are two adjustable param-
eters, which are related to the pure component molar volume
and molecular interaction energy. They are given as,
/
12
=
v
2
v
1
exp
_

z
12
z
11
R1
_
=
v
2
v
1
exp
_

^z
12
R1
_
(11)
/
21
=
v
1
v
2
exp
_

z
21
z
22
R1
_
=
v
1
v
2
exp
_

^z
21
R1
_
(12)
in which v
1
,v
2
are the molar volumes of solvent and solute,
respectively. Table 5 summarizes the molar volume for all
the compounds, which were taken from Hansens handbook
[35]. ^z
12
(dened as ^z
12
=z
12
z
22
, Eq. (11)) and ^z
21
(dened as ^z
21
=z
21
z
11
, Eq. (12)) are the cross interaction
energy parameters, (J mol
1
), which were treated as tempera-
ture independent adjustable parameters to be regressed from
the experimental data.
(2) NRTL equation. Making use of the Wilson equation and Scotts
two-liquid model of mixtures, Renon and Prausnitz [36] devel-
oped the NRTL (Non-Random Two Liquid) model, which has
been quite successful in correlating a wide variety of systems.
In this model, the liquid phase activity coefcient of the solute
is given by:
ln
2
= x
2
1
_
z
12
_
C
12
x
2
+x
1
C
12
_
2
+
z
21
C
21
(x
1
+x
2
C
21
)
2
_
(13)
Table 5
Molar volume (v), UNIQUAC volume parameter (r) and surface parameter (q) of the
pure compounds.
Compounds v (cm
3
mol
1
) r q
Benzoic acid 113.1 4.3230 3.344
Acetone 74.0 2.5735 2.336
2-Propanol 76.8 3.2491 3.124
Acetic acid 57.1 2.2024 2.072
Cyclohexane 108.7 4.0464 3.240
118 B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120
Table 6
Regression results of the Wilson, NRTL and UNIQUAC equations: parameter values, the average absolute percent deviation
AAD
and standard deviation o.
Solvent Wilson NRTL UNIQUAC
^z
12
^z
21

AAD
10
3
o
12
^g
12
^g
21

AAD
10
3
o ^u
12
^u
21

AAD
10
3
o
Acetone 1079.25 418.18 0.56 0.41 15.74 301.26 726.11 0.50 0.36 35.64 61.86 0.58 0.44
2-Propanol 2339.55 1426.33 0.60 1.67 46.53 327.00 170.08 0.26 1.03 97.78 89.83 0.74 1.93
Acetic acid 1489.20 234.55 0.96 1.20 1.18 5141.32 973.30 0.23 0.57 19.65 42.17 0.95 1.19
Cyclohexane 56.77 10082.10 8.83 2.36 16.72 3347.12 396.99 2.96 0.98 745.72 257.44 16.11 4.06
with
C
12
= exp(
12
z
12
) (14)
C
21
= exp(
21
z
21
) (15)
z
12
=
g
12
g
22
R1
=
^g
12
R1
(16)
z
21
=
g
21
g
11
R1
=
^g
21
R1
(17)
where ^g
12
(dened as ^g
12
=g
12
g
22
, Eq. (16)) and ^g
21
(dened as ^g
21
=g
21
g
11
, Eq. (17)) are two cross interaction
energy parameters (J mol
1
), which are considered as temper-
ature independent and could be regressed from experimental
data. InEqs. (14) and(15), is the parameter relatedto the non-
randomness in the mixture with
12
=
21
, which is normally
between0.2 and 0.47 as suggested by Renonand Prausnitz [36].
In this work, we treated
12
as an adjustable parameter which
was regressed from the solubility data together with ^g
12
and
^g
21
.
(3) UNIQUAC equation. Based on the local composition concept,
the lattice-based quasi-chemical model of Guggenheim and
statisticalmechanical considerations, Abrams and Prausnitz
[37] proposed the UNIQUAC (Universal Quasi-Chemical) equa-
tion to calculate activity coefcient of polar liquid mixture. In
this equation, the liquidphase activitycoefcient is dividedinto
a combinatorial part and a residual part:
ln
2
= ln
C
2
+ln
R
2
(18)
The combinatorial part of activity coefcient ln
C
2
describes the
contributions of the dominating entropies, which is determined by
the compositions and sizes of the molecules. It can be calculated
from the pure component properties,
ln
C
2
= ln
_

2
x
2
_
+
z
2
q
2
ln
_
0
2

2
_
+
1
_
l
2

r
2
r
1
l
1
_
(19)
The residual part of activity coefcient ln
R
2
describes the inter-
actions of the mixing enthalpies, which is affected not only by the
sizes of the molecules, but also by the interactions between the
solvent molecules and the solute molecules,
ln
R
2
= q
2
ln(0
2
+0
1
z
12
) +0
1
q
2
_
z
12
0
2
+0
1
z
12

z
21
0
1
+0
2
z
21
_
(20)
with

1
=
x
1
r
1
x
1
r
1
+x
2
r
2
(21)

2
=
x
2
r
2
x
1
r
1
+x
2
r
2
(22)
0
1
=
x
1
q
1
x
1
q
1
+x
2
q
2
(23)
0
2
=
x
2
q
2
x
1
q
1
+x
2
q
2
(24)
l
1
=
z
2
(r
1
q
1
) (r
1
1) (25)
l
2
=
z
2
(r
2
q
2
) (r
2
1) (26)
in which z is the coordination number usually taken as 10;
and 0 refer to the volume fraction and molecular surface fraction
for each component in the mixture, respectively. r and q are the
UNIQUAC volume parameter and surface parameter for each com-
ponent, which can be calculated fromthe Bondi group contribution
method as the sum of the group volume and area parameters [38].
The calculatedr andqvalues for eachcompoundare giveninTable 5
and the required group parameters were take for Ref. [38].
In Eq. (20), z
12
and z
21
are the interaction parameters between
the solvent and the solute, which are given by the temperature
dependence,
z
12
= exp
_

u
12
u
22
R1
_
= exp
_

^u
12
R1
_
(27)
z
21
= exp
_

u
21
u
11
R1
_
= exp
_

^u
21
R1
_
(28)
where ^u
12
(dened as ^u
12
=u
12
u
22
, Eq. (27)) and ^u
21
(dened as ^u
21
=u
21
u
11
, Eq. (28)) are two adjustable energy
parameters for each pair compounds, (J mol
1
).
Therefore, both the Wilson equation and the UNIQUAC equa-
tioncontaintwo binary energy parameters to be determined, while
the NRTL equation has three adjustable parameters. The parame-
ters for the equations were regressed from the solubility data by
minimizing the following objective function:
Minj
2
=
N
P

i=1
(ln
exp
i
ln
cal
i
)
2
(29)
where the superscripts exp and cal stand for the experimental and
the calculated activity coefcient, respectively. N
p
is the number
of data points for each system. The natural logarithm of experi-
mental activity coefcient was determined from Eq. (9) with the
experimental solubility and the melting properties of the solute.
The LevenbergMarquardt method was used as the optimization
algorithm for minimizing Eq. (29).
The optimized parameters along with the calculated average
absolute percent deviation
AAPD
and the standard deviations o
for the three activity coefcient models are listed in Table 6. The
calculated overall
AAPD
using the Wilson, NRTL and UNIQUAC
equation for the four solvents are 2.82%, 1.01% and 4.75%, respec-
tively. The UNIQUAC equation gave comparable correlation results
with the Wilson equation except for cycohexane. With an addi-
tional adjustable parameter
12
, the NRTL equation presented the
best correlation results in terms of
AAPD
.
It is worthwhile to mention that the optimized
12
values in
Table 6 are all negative except for acetic acid. In their original
paper, Renon and Prausnitz [36] related
12
to the reciprocal of
the coordinate number, which is the number of the molecules con-
nected to the reference molecular. For vaporliquid equilibrium
calculations, the range of
12
was suggested in between 0.2 and
0.47 depending on the systems and components involved. How-
ever, this ambiguous classication of the systems sometimes can
causeproblems inchoosingtheproper valueof
12
. Theexperimen-
tal results also showed that
12
is practically empirical and without
B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120 119
Table 7
Comparison of the correlation results using different processing method for the non-randomness parameter
12
.
Solvent NRTL NRTL2 NRTL3

12
^g
12
^g
21

AAD
10
3
o
12
^g
12
^g
21

AAD
10
3
o
12
^g
12
^g
21

AAD
10
3
o
Acetone 15.74 301.26 726.11 0.50 0.36 0.47 880.32 189.85 0.54 0.42 3.07 1846.33 666.64 0.46 0.35
2-Propanol 46.53 327.00 170.08 0.26 1.03 0.47 681.47 1711.41 0.51 1.59
Acetic acid 1.18 5141.32 973.30 0.23 0.57 0.47 2542.35 616.61 0.90 1.17 1.18 5141.32 973.30 0.23 0.57
Cyclohexane 16.72 3347.12 396.99 2.96 0.98 0.47 9522.47 465.15 15.19 3.11 0.70 8364.68 5259.95 12.00 2.93
Overall 1.07 4.43 4.55
a clear physical signicance [39]. On the other hand, Marina and
Tassios calculation [40] for binary and ternary vaporliquid equi-
librium showed that better accuracies could be obtained for both
miscible and immiscible systems by setting
12
=1. The theoret-
ical explanation for negative value of
12
was also given by the
authors [40]. In this work, we as well tried to correlate the activity
coefcient data using the NRTL equation with different process-
ing methods, namely NRTL (no restriction for
12
), NRTL2 (setting
0.2
12
0.47) and NRTL3 (setting
12
>0). Table 7 presents the
comparison of the correlation results by different methods. If
12
was limited within the suggested range of (0.20.47), an optimal
value of 0.47 was obtained for all the four solvents, which means
the NRTL2 equation will become a two-parameter equation by set-
ting
12
as 0.47. In this way, the obtained average absolute percent
deviation
AAPD
for each solvent is close to that of the UNIQUAC
equation, and are both lower than that from the three-parameter
NRTL equation. It should be noted that 0.47 is the upper limit
of
12
in NRTL2, and better correlation results may be obtained
if the optimized
12
is searched within a wider range. Thus the
NRTL3 equation was examined. In this case,
12
was only restricted
as a positive number, which is not conicted with the original
explanation of
12
. As expected, we got much better results in
comparison with the NRTL2 equation for acetone and acetic acid.
For 2-propanol however, no optimal positive
12
value was found
using the NRTL3 equation and no big improvement was observed
for cyclohexane.
In conclusion, as for the three-parameter models, the NRTL
equation gives slightly better correlation results than the Vant
Hoff equation. Regarding the two-parameter models investigated,
the zh equation presents comparable correlation results with the
Wilson equation, while the UNIQUAC equation shows the largest
overall average
AAPD.
Fig. 6. Extrapolations of different thermodynamic models for the solubility of ben-
zoic acid in acetic acid. Points stand for the experimental values. The lines denote
the calculated values using different thermodynamic models.
In addition, Liu et al. [14] measured the solubility of benzoic
acid in acetic acid within a wider temperature than we did. Using
their experimental data, we investigated the prediction ability of
different models. Fig. 6 shows the prediction results using differ-
ent models withour regressed parameters. The predicted solubility
curve fromthe WilsonandUNIQUACequations equallyshowexcel-
lent agreements withthe experimental data at higher temperature,
whereas the NRTL, zh and Vant Hoff equations all underestimated
thesolubility. ThoughtheVant Hoff equationhas threeparameters,
it exhibited the least accurate predictions for its empirical nature.
The extrapolation results indicate that the cross energy parameters
betweenbenzoic acidandacetic acidinthe NRTL equationare more
sensitive to temperature than those in the Wilson and UNIQUAC
equations.
4. Conclusions
The new equilibrium solubility data of benzoic acid in selected
organic solvents of acetone, 2-propanol, acetic acid and cyclohex-
ane over the temperature range of (277346) K was determined by
a gravimetric method. The solubility of benzoic acid in all the sol-
vents increases withtheraiseof temperatureandshows thehighest
increase rates with temperature in acetic acid. At a xed tempera-
ture, acetone shows the best solubility to benzoic acid followed by
2-propanol, while cyclohexane exhibits the lowest solubility. The
solubility data determined in this work agrees well the literature
data.
The measured solubility data was modeled by three-parameter
models of theVant Hoff andNRTLequations, andbytwo-parameter
models of the zh, Wilson and UNIQUAC equations. The adjustable
parameters for each model were determined by tting the solu-
bility data measured in this work. The correlation goodness order
of the models in terms of the calculated overall average abso-
lute percent deviation
AAPD
is the NRTL equation<the Vant Hoff
equation<the zh equation<the Wilson equation<the UNIQUAC
equation, which are 1.01%, 1.15%, 2.67%, 2.82% and 4.75%, respec-
tively. As for the three-parameter NRTL equation, negative values of
non-randomparameter
12
were obtained. The attempts of reduc-
ing the NRTL equation into a two-parameter model by setting
12
as the original suggested values had been made, but much higher

AAPD
were obtained. The prediction power of the models was
also investigated. The Wilson and UNIQUAC equations equally well
reproduced the experimental solubility data at higher temperature
with the parameters obtained fromthe lower temperature solubil-
ity data, which indicate that the cross energy parameters of these
two models are weak functions of temperature. The NRTL, zh and
Vant Hoff equations all underestimated the solubility.
Acknowledgements
Ms. Lyenna Wood is greatly acknowledged for her invaluable
contributions in preparing this paper. This research was supported
in part by Beijing Zhonghuan Engineering & Project Management
Co.
120 B. Long et al. / Fluid Phase Equilibria 297 (2010) 113120
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