Article

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Solubilities of Benzoic Acid in Binary Methylbenzene + Benzyl

Alcohol and Methylbenzene + Benzaldehyde Solvent Mixtures
Hui Wang,† Qinbo Wang,*,† Zhenhua Xiong,‡ Chuxiong Chen,‡ and Binwei Shen‡
†
Department of Chemical Engineering, Hunan University, Changsha, 410082 Hunan, P. R. China
‡
Zhejiang Shuyang Chemical Co. Ltd., Quzhou, 324002 Zhejiang, P. R. China

ABSTRACT: By using the synthetic method, the solubilities

of benzoic acid in binary methylbenzene + benzyl alcohol
solvent mixtures at (301.05 to 355.65) K and in binary
methylbenzene + benzaldehyde solvent mixtures at (301.05 to
354.45) K were determined at atmospheric pressure. The
studied mass fractions of benzyl alcohol and benzaldehyde in
the corresponding binary solvent mixtures range from 0.0 to
1.0. It was found that the measured solubilities increase with
the increase of temperature at constant solvent composition.
For the ternary system benzoic acid + methylbenzene + benzyl
alcohol, the results show that the binary methylbenzene + benzyl alcohol solvent mixture with the mass fraction of benzyl alcohol
at 0.80 has the best dissolving capacity for benzoic acid at constant temperature. However, for the ternary system benzoic acid +
methylbenzene + benzaldehyde, the results show that the binary methylbenzene + benzaldehyde solvent mixture with the mass
fraction of benzaldehyde of 0.20 has the best dissolving capacity for benzoic acid at constant temperature. The experimental data
were correlated by both the nonrandom two-liquid (NRTL) and the Apelblat equations, and the correlated solubilities agree
satisfactorily with the experimental observations. By coupling the Apelblat equation with the Clark and Glew equation, the
thermodynamic functions for the two studied solid−liquid equilibrium systems, including dissolution enthalpy, entropy, Gibbs
energy, and isobaric heat capacity, were calculated and discussed.

1. INTRODUCTION essential to obtain the solubility data of benzoic acid in

Benzoic acid, benzyl alcohol, and benzaldehyde are all
important fine chemicals. They are widely used in the field of
pharmaceutical, perfumery, dyestuff, and agrichemicals, etc.
Commercially, they are manufactured by the air oxidation of
methylbenzene.1,2 The oxidized mixtures include the products
benzoic acid, benzyl alcohol, and benzaldehyde, and the
unreacted methylbenzene. Sequentially, the method of
distillation would be used to separate the reacted mixture.
Because of the higher boiling temperature of benzyl alcohol and
benzaldehyde, the distillation temperature is usually higher than
400 K. At this operation condition, the product benzoic acid is
prone to esterification with benzyl alcohol, which might result
in another byproduct benzyl benzoate that makes the
separation process difficult and complex.
Alternatively, one may expect to separate most of the benzoic
acid from the reaction mixtures first, and then use the method
of distillation to separate the remaining mixtures. Usually
crystallization is the preferred method to separate benzoic acid
from the reaction mixtures.3 In this sense, the solubility data of
benzoic acid in benzyl alcohol + methylbenzene and
benzaldehyde + methylbenzene solvent mixtures are essential
for the proper separation process design. Unfortunately, besides
some reports on the solubility of benzoic acid in pure water4−8
and in pure methylbenzene,9,10 no reports on the solubility of
benzoic in benzyl alcohol or benzaldehyde could be found, let
alone that in the above-mentioned solvent mixtures. Thus, it is
methylbenzene + benzyl alcohol and methylbenzene +
benzaldehyde.
In this work, by using the synthetic method, the solubilities
of benzoic acid in binary methylbenzene + benzyl alcohol
mixtures and methylbenzene + benzaldehyde mixtures at
different temperatures were measured. The effects of mass
fraction of benzyl alcohol and benzaldehyde in the correspond-
ing solvent mixtures at (0.0 to 1.00) on the solubilities were
studied. The experimental data were correlated by both the
NRTL model11 and the Apelblat equation. The model
parameters were regressed, and the correlated solubilities
agree satisfactorily with the experimental observations. By
coupling the Apelblat equation with the Clark and Glew
equation, the thermodynamic functions for the two studied
solid−liquid equilibrium systems, including dissolution en-
thalpy, entropy, Gibbs energy, and isobaric heat capacity, were
calculated and discussed.
2. EXPERIMENTAL SECTION
2.1. Materials. Benzoic acid, methylbenzene, benzyl
alcohol, and benzaldehyde were obtained from Aladdin
Chemistry Co., and had a declared purity of >0.990 in mass
Received: August 20, 2014
Accepted: December 22, 2014

© XXXX American Chemical Society A DOI: 10.1021/je500775r

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 1. Suppliers and Mass Fraction Purity of the Materials

chemical name suppliers mass fraction electrical resistivity/MΩ·cm analysis method
benzoic acid Aladdin Chemistry Co. > 0.995 HPLCa
methylbenzene Aladdin Chemistry Co. > 0.990 GCb
benzyl alcohol Aladdin Chemistry Co. > 0.990 GCb
benzaldehyde Aladdin Chemistry Co. > 0.985 GCb
water Hangzhou Wahaha Group Co. 18.2c
a b c
High-performance liquid chromatography. Gas chromatograph. Pure water resistivity measuring instrument.

fraction. The mass fraction purity of benzoic acid was checked To verify the repeatability of the experimental data, each data
by high-performance liquid chromatography (HPLC). The point of the experimental solubility was measured at least two
mass fraction purities of methylbenzene, benzyl alcohol, and times, and the uncertainty of each saturated temperature was
benzaldehyde were checked by gas chromatography (GC). within ± 0.05 K.
Purified water was obtained from Hangzhou Wahaha Group
Co., and had the reported electrical resistivity of 18.2 MΩ·cm, 3. RESULTS AND DISCUSSION
which falls into the category of ultrapure water. All the 3.1. Validation of the Experimental Technique. To
chemicals were used without further purification. The suppliers check the reliability of the experimental technique, the
and the mass fraction of the used chemical reagents are shown solubilities of benzoic acid in pure water were measured, and
in Table 1. the experimental solubility data are listed in Table 2 along with
2.2. Apparatus and Procedures. The solubilities of
benzoic acid in methylbenzene + benzyl alcohol mixtures and Table 2. Solubilities of Benzoic Acid (cr,1) in Water at
methylbenzene + benzaldehyde mixtures were measured by a Different Temperatures and p = 101.3 kPaa
synthetic method. The laser technique was used, and the
T/K S/(g(100g)−1) RD1 % RD2 % RD3 % RD4 %
experimental principle and technique have been introduced in
detail by Chen and Jiang et al.12,13 Briefly, the main apparatus 298.85 0.337 1.157 0.564 1.157 1.454
include a solid−liquid equilibrium cell, a laser-detecting system, 305.95 0.431 1.671 0.975 −0.418 −0.418
a temperature-controlling and measurement system, and a 312.85 0.540 3.129 0.352 1.648 1.092
magnetic stirring system. The equilibrium cell is approximately 319.35 0.679 4.348 0.516 0.516 0.516
150 mL. The cell was heated in a thermostatic water bath and 323.25 0.826 1.586 0.012 1.102 0.618
the equilibrium temperature was determined by a mercury 329.55 1.026 4.150 −0.721 −0.721 0.253
thermometer with an uncertainty of ± 0.05 K. The mixture was 335.25 1.271 1.196 0.645 −0.220 0.803
stirred by a magnetic agitator to accelerate the dissolution of 340.25 1.560 1.384 0.487 −0.474 1.192
a
benzoic acid.14,15 Standard uncertainties u are u(T) = 0.05 K, ur(p) = 0.05, ur(S) = 0.04.
In each experiment, carefully preweighed amounts of the S is the measured solubility of benzoic acid in water; RD1 %, RD2 %,
solute and solvent were placed in the equilibrium cell. All the RD3 %, and RD4 % are the relative deviations of our determined
solubility with the literature data from Apelblat,6 Lee,4 Oliveria,5 and
chemicals were weighted by an electronic analytical balance Liu,7 respectively. The solubility is defined as the mass of solute (g) in
(type AL204, Mettler Toledo instrument Co. Ltd., uncertainty 100 g of solvent.
of ± 0.0001 g). The cell was then put into a thermostatic water
bath, and the mixture was continuously stirred. The temper-
the relative deviations between experimental data and literature
ature of the mixture was then increased in a continuous fashion data.4−7 Figure 1 is also provided to show the result. From
(2.5 K/h) until the benzoic acid was dissolved. Near the Table 2 and Figure 1, a fairly good agreement was obtained
dissolution temperature, the temperature increase was typically between the experimentally determined and literature reported
kept at 0.2 K/h or slower.
The laser monitoring equipment was used to monitor the
dissolution condition of the solution. A steady laser beam was
passed through the solvent−solute mixture and received by a
laser power meter. If there were solids in the path of the beam,
it would be scattered and the transmitted intensity would be
reduced. The intensity of the transmitted laser light is recorded
by a computer in terms of the photovoltage. The corresponding
temperature at a given composition is determined as the one at
which the solid phase just disappears.
The method of calculating the solubility data was the ratio
method. The solubility is defined as the mass of solute in 100 g
of solvent. In this paper, the solubility was calculated by the
following equation:
m1
S= 100
m2 (1) Figure 1. Comparisons between experimental solubility of benzoic
acid in water with that reported in literature: □, literature data from
where S is the solubility of the solute; m1 and m2 are the mass of Lee;4 ○, literature data from Liu;7 △, literature data from Oliveria;5
solute and solvent in the saturated solution, respectively. ▽, literature data from Apelblat;6 ●, experimental data.

B DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

data. The agreement with published data suggests that the that the measured solubility data increases with increasing
technique is reliable. temperature.
To further verify the reliability of the experimental results, To illustrated the effect of solvent composition on the
the solubility data of benzoic acid in pure methylbenzene was solubilites more apparently, the solubility data of benzoic acid
measured. The determined experimental data are listed in Table in methylbenzene + benzyl alcohol and methylbenzene +
3 and plotted in Figure 2, along with the relative deviations benzaldehyde binary mixtures at (303.15 to 353.15) K were
predicted by the NRTL model using the regressed model
Table 3. Solubilities of Benzoic Acid (cr,1) in parameters listed in Table 6. The results are shown in Figures 5
Methylbenzene at Different Temperatures and p = 101.3 and 6. From Figure 5 it can also be seen that at each measured
kPaa temperature, binary methylbenzene + benzyl alcohol solvent
mixtures with a mass fraction of benzyl alcohol at 0.80 usually
T/K S/(g(100g)−1) RD1 % RD2 %
has the best dissolving capacity for benzoic acid. It indicates
301.05 11.33 −3.24 −3.24 that the higher or the lower the mass fraction of benzyl alcohol
306.05 13.17 −0.36 −3.63 is, the less is the solubility. In other words, within this mass
311.75 16.16 −1.49 −5.58 fraction of benzyl alcohol range, there is a slope presenting the
316.95 19.81 −0.75 1.27 change of solubility influenced by solvent concentrations at
323.35 24.46 −0.62 2.32 each measured temperature. This maximum-solubility effect has
330.25 30.14 −0.25 0.51 also been noticed by Chen and Ma for the solubility of
336.55 37.91 −0.76 −3.90 terephthalic acid in the mixture of acetic acid and water,12 and
340.75 47.65 −1.23 0.01 Wang et al. for the solubility of phthalic acid in the mixture of
344.65 58.82 −1.04 1.96 acetic acid + wate,16 and the solubility of adipic acid and
348.25 71.53 −0.61 0.74 succinic acid in the mixture of acetic acid + water.26,27 Similar
351.35 86.16 −0.16 0.73 maximum-solubility effects also could be found for the
354.05 102.6 −0.62 0.40 solubility of benzoic acid in binary methylbenzene +
a
Standard uncertainties u are u(T) = 0.05 K, ur(p) = 0.05, ur(S) = 0.04. benzaldehyde mixtures. From Figure 6, it can be seen that at
S is the measured solubility of benzoic acid in methylbenzene; RD1 % each measured temperature, binary methylbenzene + benzalde-
and RD2 % are the relative deviations of our determined solubility with hyde solvent mixtures with a mass fraction of benzaldehyde at
the literature data from Thati9 and Chipman,10 respectively. The 0.20 usually has the best dissolving capacity for benzoic acid.
solubility is defined as the mass of solute (g) in 100 g of solvent.
3.3. Correlation of Experimental Data. Generally, solid−
liquid equilibrium without solid−solid phase transition can be
approximated by eq 1:
ΔfusH ⎛ 1 1 ⎞
ln(γ1x1) = − ⎜ − ⎟
R ⎝T Tfus ⎠ (2)
where ΔfusH is the molar fusion enthalpy of solute, Tfus is the
fusion temperature, T is the absolute temperature, R is the
universal gas constant, γ1 is the activity coefficient of solute, and
x1 is the real mole fraction of solute in solution. In this
equation, the enthalpy of melting is assumed to be independent
of temperature. Because the activity coefficient γ1 depends on
the solution composition and temperature, eq 1 must be solved
iteratively. For the calculation of the activity coefficient, the
NRTL activity coefficient model was used in this work as
Figure 2. Comparisons between experimental solubility of benzoic 3 3
acid in methylbenzene with that reported in literature: □, literature ∑ j = 1 τjiGjixj xjGij
data from Thati;9 ○, literature data from Chipman;10 ●, experimental ln γi = 3
+ ∑ 3
·
∑k = 1 Gkixk j = 1 ∑k = 1 Gkjxk
data.
⎛ ∑ xτ G ⎞
3
⎜τ − k = 1 k kj kj ⎟
between experimental data and literature data.9,10 It can be ⎜ ij ∑k = 1 Gkjxk ⎟⎠
3
⎝ (3)
found that the obtained experimental data have no important
deviations with the literature data. The agreement with bij
published data further suggests that the technique is reliable. τij = aij +
3.2. Experimental Solubility Data. The measured T (4)
solubilities of benzoic acid in methylbenzene + benzyl alcohol Gij = exp( −αijτij) (5)
mixtures are shown in Table 4 and Figure 3, and the measured
solubilities of benzoic acid in methylbenzene + benzaldehyde αij = αji , τij ≠ τji , τii = 0 (6)
mixtures are summarized in Table 5 and Figure4. In these
tables and figures, w3 is defined as the mass fraction of benzyl where T is the absolute temperature; γi is the activity coefficient
alcohol in binary methylbenzene + benzyl alcohol and benzoic of component i; aij and bij are the NRTL binary interaction
acid in binary methylbenzene + benzaldehyde solvent mixtures, parameters.
and T and S represent the absolute temperature and the To calculate the solubility, fusion temperature (Tfus) and
measured solubility data, respectively. The results clearly show molar enthalpy of fusion of solute (ΔfusH) are required. Tfus and
C DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. Solubilities and Thermodynamic Functions of Benzoic Acid (cr,1) in Methylbenzene (2) + Benzyl Alcohol (3) Solvent
Mixtures at Different Temperatures and p = 101.3 kPaa
T S Sc,1 RD1 Sc,2 RD2 ΔHT0 ΔGT0 ΔST0 ΔCp0 ζH ζTS
−1 −1 −1 −1b −1c −1 −1d
K g(100g) g(100g) % g(100g) % kJ·mol kJ·mol J·mol ·K J·mol−1·K−1e % %
w3 = 0.0
301.05 11.33 11.09 −2.07 11.01 2.79 36.77 22.21 48.35 280.1 71.64 28.36
306.05 13.33 13.06 −2.01 13.09 1.80 38.10 22.51 50.94 70.96 29.04
311.75 16.32 16.18 −0.88 15.92 2.47 39.61 22.99 53.31 70.44 29.56
316.95 19.97 20.13 0.78 19.86 0.55 40.96 23.57 54.87 70.20 29.80
322.65 24.62 25.35 2.95 23.91 2.90 42.46 24.25 56.42 69.99 30.01
328.25 30.30 30.85 1.82 31.09 −2.61 43.93 24.99 57.68 69.88 30.12
334.55 38.07 37.89 −0.47 37.06 2.65 45.61 25.84 59.09 69.76 30.24
339.85 47.81 47.54 −0.56 48.02 −0.44 47.06 26.71 59.90 69.81 30.19
344.65 58.99 59.20 0.36 59.03 −0.07 48.45 27.41 61.05 69.72 30.28
348.25 71.69 73.67 2.76 70.08 2.25 49.58 27.96 62.10 69.63 30.37
351.35 86.33 86.21 −0.14 86.13 0.23 50.66 28.29 63.66 69.37 30.63
354.05 102.78 101.5 −1.24 102.2 0.61 51.70 28.39 65.83 68.92 31.08
w3 = 0.2
303.35 19.70 19.64 −0.30 19.58 0.62 36.87 28.77 26.71 286.3 81.98 18.02
307.45 21.92 21.80 −0.57 21.69 1.05 38.01 28.86 29.75 80.60 19.40
312.75 25.35 25.25 −0.39 24.96 1.52 39.50 28.99 33.58 79.00 21.00
317.35 29.77 29.62 −0.50 29.39 1.27 40.80 29.17 36.67 77.81 22.19
321.75 34.81 34.56 −0.73 34.09 2.07 42.07 29.31 39.66 76.73 23.27
327.85 41.79 41.77 −0.07 41.22 1.38 43.87 29.39 44.16 75.19 24.81
333.05 50.25 49.96 −0.58 51.06 −1.61 45.46 29.42 48.16 73.92 26.08
338.55 60.26 59.84 −0.70 59.63 1.04 47.20 30.01 52.83 72.52 27.48
343.35 72.11 70.69 −1.97 71.08 1.43 48.82 31.16 57.44 71.23 28.77
348.75 85.75 84.36 −1.63 86.03 −0.33 50.68 31.66 63.14 69.01 30.29
w3 = 0.4
301.55 22.60 22.82 0.96 22.91 −1.35 36.48 25.70 19.15 304.9 86.34 13.66
304.85 25.06 24.98 −0.30 25.19 −0.53 37.47 26.80 22.40 84.59 15.41
310.05 28.55 28.25 −1.05 28.03 1.82 39.04 27.73 27.53 82.06 17.94
316.65 34.43 33.83 −1.74 34.01 1.22 41.08 28.58 34.18 79.15 20.85
323.05 42.42 41.19 −2.90 41.58 1.98 43.12 29.29 40.97 76.52 23.48
330.95 52.72 51.49 −2.32 51.29 2.70 45.71 29.89 49.60 73.58 26.42
337.55 64.89 63.15 −2.68 64.31 0.90 47.99 30.26 57.50 71.20 28.80
343.45 79.09 76.34 −3.48 79.19 −0.13 50.13 30.51 65.24 69.11 30.89
348.25 95.21 92.93 −2.39 96.01 −0.84 52.00 30.65 72.38 67.35 32.65
353.45 113.47 112.97 −0.44 114.9 −1.22 54.06 30.71 80.25 65.59 34.41
w3 = 0.6
303.35 25.99 26.39 1.55 25.68 1.18 37.72 22.01 28.50 329.5 81.35 18.65
307.35 28.44 28.63 0.64 28.01 1.53 39.03 23.05 33.17 79.29 20.71
311.55 32.00 31.86 −0.45 31.88 0.38 40.43 24.02 38.25 77.24 22.76
317.45 37.69 37.18 −1.33 37.06 1.66 42.43 24.94 45.48 74.61 25.39
323.45 44.67 43.87 −1.79 44.06 1.36 44.51 25.83 53.04 72.18 27.82
329.15 52.66 51.64 −1.93 52.13 1.01 46.53 26.63 60.46 70.04 29.96
334.55 61.89 60.66 −1.99 61.02 1.41 48.50 27.35 67.77 68.15 31.85
339.65 72.73 71.10 −2.24 72.38 0.48 50.42 27.99 75.01 66.43 33.57
344.25 84.73 82.49 −2.64 85.19 −0.54 52.21 28.52 81.88 64.94 35.06
348.95 97.73 95.96 −1.82 99.01 −1.31 54.07 28.84 88.89 63.54 36.46
w3 = 0.8
307.85 26.77 27.07 1.11 26.86 −0.32 40.58 23.74 54.72 361.0 70.67 29.33
310.45 29.07 30.10 3.53 29.39 −1.10 41.53 23.47 58.17 69.70 30.30
314.25 33.56 34.11 1.65 34.21 −1.94 42.94 23.02 63.40 68.31 31.69
318.85 39.98 39.68 −0.75 39.86 0.31 44.67 22.41 69.83 66.74 33.26
323.85 47.04 45.99 −2.24 46.68 0.76 46.57 21.72 76.71 65.21 34.79
328.55 55.22 53.12 −3.80 54.62 1.08 48.37 20.99 83.34 63.86 36.14
333.25 64.45 63.29 −1.81 63.88 0.89 50.21 20.21 90.00 62.60 37.40
338.35 74.73 72.24 −3.34 74.01 0.97 52.20 19.35 97.11 61.37 38.63
343.55 87.02 84.59 −2.79 88.19 −1.35 54.27 18.39 104.43 60.20 39.80
349.75 101.28 101.17 −0.11 103.1 −1.78 56.73 17.26 112.87 58.97 41.03

D DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. continued
T S Sc,1 RD1 Sc,2 RD2 ΔHT0 ΔGT0 ΔST0 ΔCp0 ζH ζTS
K g(100g)−1 g(100g)−1 % g(100g)−1 % kJ·mol −1b
kJ·mol −1c
J·mol−1·K −1d
J·mol−1·K−1e % %
w3 = 1.0
306.35 29.78 28.61 −3.93 29.26 1.74 42.12 14.63 89.73 403.7 60.51 39.49
309.05 31.57 30.52 −3.32 31.82 −0.80 43.21 14.39 93.27 59.98 40.02
312.75 34.00 33.17 −2.43 33.86 0.42 44.71 14.03 98.08 59.31 40.69
316.25 37.38 36.47 −2.45 37.02 0.97 46.12 13.68 102.57 58.71 41.29
321.75 42.32 41.53 −1.87 43.52 −2.83 48.34 13.10 109.53 57.83 42.17
327.45 48.48 47.69 −1.63 49.06 −1.19 50.64 12.45 116.62 57.01 42.99
332.85 55.29 54.46 −1.49 54.68 1.10 52.82 11.80 123.23 56.29 43.71
338.55 64.28 63.22 −1.64 63.88 0.62 55.12 11.08 130.08 55.59 44.41
343.05 73.26 71.87 −1.90 71.16 2.87 56.94 10.49 135.41 55.07 44.93
347.25 82.91 81.65 −1.52 81.09 2.19 58.63 9.91 140.33 54.61 45.39
351.75 94.14 94.78 0.68 95.18 −1.10 60.45 9.26 145.52 54.15 45.85
355.65 106.42 107.45 0.97 107.3 −0.86 62.03 8.69 149.98 53.76 46.24
a
Standard uncertainties u are u(T) = 0.05 K, ur(p) = 0.05, ur(S) = 0.04. The solubility is defined as the mass of solute (g) in 100 g of solvent. w3 is
the mass fraction of benzyl alcohol in binary methylbenzene + benzyl alcohol solvent mixtures. Sc,1 and RD1 represent the NRTL model correlated
solubility data and the relative deviation between the correlated and experimental determined solubilities, respectively. Sc,2 and RD2 represent the
Apelblat equation correlated solubility data and the relative deviation between the correlated and experimental determined solubilities, respectively.
b
Calculated by eq 13. cCalculated by eq 15. dCalculated by eq 14. eCalculated by eq 12.

where n is the total number of experimental points, Sci and Si

Figure 3. Solubility data of benzoic acid (cr,1) in methylbenzene (2) +
benzyl alcohol (3) solvent mixtures: ■, w3 = 0.0; ●, w3 = 0.2; ▲, w3 =
0.4; ▼, w3 = 0.6; ◀, w3 = 0.8; ▶, w3 = 1.0. w3 is the mass fraction of
benzyl alcohol in binary methylbenzene + benzyl alcohol solvent
mixtures.
ΔfusH used in the calculation are 395.6 K and 17316 J·mol−1,
which are obtained from the literature.17
Using model eqs 1 to 5, the measured solubilities were
correlated, and the model parameters were optimized. As
Renon and Prausnitz proposed, in the optimization, αij was
chosen as 0.3.11 The optimum algorithm applied in the
parameter estimation program was the Nelder−Mead Simplex
approach.17 Function f minsearch in the optimization toolbox of
Matlab (Mathwork, MA) uses the Nelder−Mead Simplex
approach and can be employed for the minimization of the
objective function, which is the averaged relative deviation
(ARD) between the experimental and calculated solubility
defined by
n
1
ARD = ∑ abs(RDi)
n i=1 (7)
S − Si
RDi = ci 100
Si (8)
are the ith calculated and experimental solubility. The
correlated results and the corresponding RD are given in
Table 4 and Table 5. The optimized model parameters and the
averaged relative deviation (ARD) defined are given in Table 6.
Generally satisfactorily agreement between the experimental
and correlated data were obtained. This indicates that the
NRTL model equation could be used to correlate the solubility
of benzoic acid in methylbenzene + benzyl alcohol mixtures
and methylbenzene + benzaldehyde mixtures.
The thermodynamic functions are important for the solid−
liquid equilibrium for ternary benzoic acid + methylbenzene +
benzyl alcohol and benzoic acid + methylbenzene +
benzaldehyde system. The obtained NRTL model parameters
could moderately supplement the NRTL databank of basic
binary interaction parameters. However, it is difficult to derive
the thermodynamic functions directly from the NRTL model.
Further, a very convenient operational model of engineering
interest to calculate the solubility of benzoic acid without
bothering with the NRTL model is desired. Thus, the modified
Apelblat equation was also used to correlate the experimental
solubilities of benzoic acid in methylbenzene + benzyl alcohol
binary mixtures and methylbenzene + benzaldehyde binary
mixtures,18,19 which was previously proposed by Apelblat to
describe the relationship between the mole fraction of solute
and temperature for saturated solution, and the expression is
B
ln x1 = A + + C ln T
T (9)
where x1 is the mole fraction of benzoic acid, T is the absolute
temperature, and A, B, and C are the empirical model
parameters. To use eq 9 correlating the solubility of benzoic
acid at different solvent compositions, the following empirical
correlations were adopted:20
A = A 0 + A1x 2 + A 2 x 2 2
B = B0 + B1x 2 + B2 x 2 2
C = C0 + C1x 2 + C2x 2 2 (10)

E DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 5. Solubilities and Thermodynamic Functions of Benzoic Acid (cr,1) in Methylbenzene (2) + Benzaldehyde (3) Solvent
Mixtures at Different Temperatures and p = 101.3 kPaa
T S Sc,1 RD1 Sc,2 RD2 ΔHd ΔGd ΔSd ΔCp0 ζH ζTS
−1 −1 −1 −1b −1c −1 −1d
K g(100g) g(100g) % g(100g) % kJ·mol kJ·mol J·mol ·K J·mol−1·K−1e % %
w3 = 0.0
301.05 11.33 11.09 −2.07 10.98 3.09 18.92 11.65 24.14 284.4 72.25 27.75
306.05 13.33 13.06 −2.01 13.05 2.10 20.29 11.89 27.46 70.71 29.29
311.75 16.32 16.18 −0.88 15.87 2.77 21.88 12.24 30.90 69.43 30.57
316.95 19.97 20.13 0.78 19.80 0.85 23.35 12.68 33.68 68.63 31.37
323.35 24.62 25.35 2.95 23.84 3.20 25.00 13.19 36.61 67.91 32.09
330.25 30.30 30.85 1.82 31.00 −2.31 26.67 13.76 39.33 67.38 32.62
336.55 38.07 37.89 −0.47 36.95 2.95 28.62 14.46 42.33 66.89 33.11
340.75 47.81 47.54 −0.56 47.88 −0.14 30.38 15.24 44.55 66.74 33.26
344.65 58.99 59.20 0.36 58.85 0.23 32.07 15.98 46.69 66.59 33.41
348.25 71.69 73.67 2.76 69.86 2.55 33.49 16.69 48.24 66.59 33.41
351.35 86.33 86.21 −0.14 85.87 0.53 34.83 17.34 49.77 66.57 33.43
354.05 102.78 101.50 −1.24 101.8 0.91 36.10 17.90 51.41 66.48 33.52
w3 = 0.2
307.95 13.46 13.56 0.69 13.34 0.92 21.20 16.02 16.84 305.3 80.35 19.65
312.85 15.94 15.88 −0.38 15.73 1.35 22.64 16.20 20.59 77.86 22.14
317.25 19.87 19.72 −0.74 19.50 1.82 23.98 16.52 23.53 76.26 23.74
321.85 24.92 24.63 −1.15 24.53 1.57 25.42 16.89 26.52 74.86 25.14
326.75 31.76 31.18 −1.81 31.00 2.37 27.02 17.33 29.66 73.60 26.40
332.25 40.14 39.27 −2.18 39.47 1.68 28.86 17.76 33.41 72.22 27.78
337.25 50.78 49.27 −2.98 51.45 −1.31 30.65 18.22 36.87 71.14 28.86
342.35 63.55 61.43 −3.34 62.70 1.34 32.57 18.62 40.72 70.02 29.98
346.95 78.64 75.51 −3.99 77.28 1.73 34.42 18.97 44.51 69.03 30.97
351.65 95.88 92.29 −3.75 96.54 −0.68 36.38 19.21 48.82 67.94 32.06
w3 = 0.4
307.75 10.47 10.43 −0.42 10.58 −1.05 21.60 20.06 8.54 327.0 89.15 10.85
312.65 12.87 12.74 −0.96 12.99 −0.96 23.15 20.07 13.04 85.02 14.98
317.45 17.20 17.06 −0.81 16.84 2.12 24.72 20.05 17.22 81.89 18.11
323.85 23.39 23.27 −0.48 23.03 1.52 26.86 19.99 22.89 78.37 21.63
329.65 31.83 31.66 −0.55 31.11 2.28 28.91 19.86 28.02 75.78 24.22
335.25 42.19 41.75 −1.04 40.92 3.00 30.97 19.67 33.16 73.59 26.41
340.45 54.23 53.33 −1.66 53.58 1.20 32.99 19.45 38.18 71.74 28.26
345.55 67.59 66.59 −1.48 67.48 0.17 35.04 19.26 43.39 70.04 29.96
349.75 82.43 80.96 −1.79 82.88 −0.54 36.84 19.07 47.96 68.71 31.29
352.95 98.85 95.42 −3.47 99.76 −0.92 38.33 18.97 51.76 67.72 32.28
w3 = 0.6
307.35 9.70 9.63 −0.66 9.55 1.48 22.08 21.03 3.41 357.7 95.46 4.54
312.35 12.14 12.00 −1.15 11.92 1.83 23.82 21.05 8.87 89.58 10.42
317.95 16.27 16.12 −0.91 16.16 0.68 25.82 21.07 14.94 84.46 15.54
324.25 22.36 22.29 −0.32 21.92 1.96 28.12 21.05 21.79 79.92 20.08
329.25 29.95 29.84 −0.36 29.46 1.66 30.02 21.03 27.31 76.95 23.05
337.45 39.46 40.14 1.71 38.94 1.31 33.14 20.86 36.39 72.97 27.03
342.25 50.60 51.41 1.62 49.73 1.71 35.12 20.75 41.99 70.96 29.04
346.65 62.79 63.77 1.56 62.30 0.78 36.99 20.60 47.28 69.30 30.70
350.75 75.84 77.31 1.93 76.03 −0.24 38.77 20.42 52.34 67.87 32.13
354.45 90.35 92.40 2.27 91.26 −1.01 40.44 20.22 57.06 66.66 33.34
w3 = 0.8
305.35 6.51 6.54 0.55 6.52 −0.21 22.03 21.68 1.17 396.8 98.41 1.59
310.65 9.15 9.04 −1.19 9.22 −0.80 24.11 21.65 7.92 90.74 9.26
316.75 13.31 13.15 −1.18 13.52 −1.64 26.52 21.57 15.63 84.27 15.73
322.35 18.63 18.54 −0.46 18.52 0.61 28.77 21.45 22.71 79.72 20.28
327.95 24.99 25.06 0.27 24.73 1.06 31.05 21.28 29.78 76.07 23.93
333.35 33.07 33.28 0.63 32.61 1.38 33.29 21.08 36.64 73.16 26.84
338.35 42.57 42.81 0.56 42.07 1.19 35.41 20.84 43.05 70.85 29.15
343.35 52.66 53.25 1.13 51.99 1.27 37.55 20.57 49.45 68.86 31.14
348.25 64.69 65.94 1.94 65.36 −1.05 39.68 20.26 55.76 67.14 32.86
352.75 78.83 80.94 2.68 80.00 −1.48 41.69 19.94 61.65 65.72 34.28

F DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 5. continued
T S Sc,1 RD1 Sc,2 RD2 ΔHd ΔGd ΔSd ΔCp0 ζH ζTS
K g(100g)−1 g(100g)−1 % g(100g)−1 % kJ·mol −1b
kJ·mol −1c
J·mol−1·K −1d
J·mol−1·K−1e % %
w3 = 1.0
307.45 5.64 5.72 1.48 5.53 2.04 23.78 20.57 10.44 449.37 88.11 11.89
310.95 7.39 7.38 −0.22 7.43 −0.50 25.36 20.53 15.52 84.01 15.99
315.05 9.99 9.88 −1.02 9.91 0.72 27.20 20.45 21.41 80.13 19.87
319.35 13.21 13.21 0.00 13.04 1.27 29.13 20.35 27.50 76.84 23.16
322.95 17.09 17.25 0.95 17.52 −2.53 30.75 20.24 32.54 74.53 25.47
327.05 21.95 22.64 3.16 22.14 −0.89 32.59 20.10 38.21 72.29 27.71
331.65 27.63 27.64 0.07 27.24 1.40 34.66 19.91 44.48 70.14 29.86
334.95 33.97 34.33 1.07 33.65 0.92 36.14 19.75 48.93 68.80 31.20
339.55 41.27 41.05 −0.54 39.96 3.17 38.21 19.51 55.06 67.14 32.86
343.35 49.16 50.37 2.46 47.93 2.49 39.92 19.29 60.06 65.93 34.07
347.35 57.91 58.30 0.67 58.38 −0.80 41.71 19.04 65.27 64.79 35.21
350.55 67.41 69.14 2.57 67.78 −0.56 43.15 18.83 69.39 63.95 36.05
a
Standard uncertainties u are u(T) = 0.05 K, ur(p) = 0.05, ur(S) = 0.04. The solubility is defined as the mass of solute (g) in 100 g of solvent. w3 is
the mass fraction of benzyl alcohol in binary methylbenzene + benzyl alcohol solvent mixtures. Sc,1 and RD1 represent the NRTL model correlated
solubility data and the relative deviation between the correlated and experimental determined solubilities, respectively. Sc,2 and RD2 represent the
Apelblat equation correlated solubility data and the relative deviation between the correlated and experimental determined solubilities, respectively.
b
Calculated by eq 13. cCalculated by eq 15. dCalculated by eq 14. eCalculated by eq 12.

Figure 4. Solubility data of benzoic acid (cr,1) in methylbenzene (2) +
benzaldehyde (3) solvent mixtures: ■, w3 = 0.0; ●, w3 = 0.2; ▲, w3 =
0.4; ▼, w3 = 0.6; ◀, w3 = 0.8; ▶, w3 = 1.0. w3 is the mass fraction of
benzaldehyde in binary methylbenzene + benzaldehyde solvent
mixtures.
Figure 5. Solubility data of benzoic acid (cr,1) in methylbenzene (2) +
benzyl alcohol (3) solvent mixtures: ■, 303.15 K; ●, 313.15 K; ▲,
323.15 K; ▼, 333.15K; ◀, 343.15K; ▶, 353.15 K. w3 is the mass
fraction of benzyl alcohol in binary methylbenzene + benzyl alcohol
solvent mixtures.

Table 6. Optimized Temperature-Independent Binary

Interaction Parameters for the NRTL Model for Benzoic
Acid (1) + Methylbenzene(2) + Benzyl Alcohol (3) +
Benzaldehyde (4)
i−j aij aji bij/K bji/K ARD/%
1−2 0.948 6.232 −239.9 −203.9 3.68
1−3 4.820 −0.162 −1889 1540
1−4 5.007 −7.858 −1933 3983
2−3 −0.868 1.417 128.7 370.3
2−4 −3.058 −5.348 4557 1814
3−4 4.668 −2.619 −889.2 505.7

where x 2 is the mole fraction of methylbenzene in
methylbenzene + benzyl alcohol mixtures or in methylbenzene
+ benzaldehyde mixtures; Ai, Bi, and Ci are model parameters.
Using model eqs 9 to 10, the measured solubilities were
correlated, and the model parameters were optimized. The
optimum algorithm applied in the parameter estimation
program was the same as that used in the NRTL correlation.
G DOI: 10.1021/je500775r
Figure 6. Solubility data of benzoic acid (cr,1) in methylbenzene (2) +
benzaldehyde (3) solvent mixtures: ■, 303.15 K; ●, 313.15 K; ▲,
323.15 K; ▼, 333.15 K; ◀, 343.15 K; ▶, 353.15 K. w3 is the mass
fraction of benzaldehyde in binary methylbenzene + benzaldehyde
solvent mixtures.
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

The correlated results and the corresponding RD are given in Similarly for the dissolution entropy ΔS0T at the measured
Table 4 and Table 5. The optimized model parameters and the temperature, the relationship for ΔS0θ with temperature could
averaged relative deviation (ARD) defined are given in Table 7 be given by

Table 7. Apelblat Model Parameters for Ternary Benzoic T ΔC p0

Acid (1) + Methylbenzene (2) + Benzyl Alcohol (3) System
ΔST0 = ΔSθ0 + ∫θ T
dT = R(A + C + C ln T )
(14)
Ai Bi/K Ci ARD/%
i=0 −315.8 9810 48.56 2.94 The values of Gibbs free energy can be calculated by the
i=1 215.1 −9545 −36.25 equation:
i=2 −118.6 5446 21.51
ΔGT0 = ΔHT0 − T ΔST0 (15)
To compare the relative contribution to the standard Gibbs
energy by enthalpy (ζH %) and entropy (ζTS %) in the
Table 8. Apelblat Model Parameters for Ternary Benzoic dissolving process, eq 16 and eq 17 were employed.23−25
Acid (1) + Methylbenzene (2) + Benzaldehyde System
|ΔHT0|
Ai Bi/K Ci ARD/% ζH% = 100
|ΔHT0| + |T ΔST0| (16)
i=0 −362.4 13757 54.05 3.28
i=1 254.4 −11315 −38.65
i=2 −101.5 4871 16.40
|T ΔST0|
ζTS% = 100
|ΔHT0| + |T ΔST0| (17)
The calculated values of ζH % and ζTS % are also listed in Table
and Table 8. Generally satisfactorily agreement between the 4 and Table 5. The results show that in all cases the main
experimental and correlated data were also obtained. It contributor to standard Gibbs energy of the dissolving process
indicates that the Apelblat equation could also be used to of benzoic acid in methylbenzene + benzyl alcohol solvent
correlate the solubility of benzoic acid in methylbenzene + mixtures and methylbenzene + benzaldehyde solvent mixtures
benzyl alcohol mixtures and methylbenzene + benzaldehyde is the enthalpy. With the increase of temperature or the
mixtures. increasing mass fraction of benzyl alcohol or benzaldehyde in
3.4. Thermodynamic Functions of the Solution. To solvent mixtures, the contribution of enthalpy to standard
evaluate standard thermodynamic functions from solubility Gibbs energy gradually decreases.
data, here the approach originally proposed by Clark and The thermodynamic parameters of solution, ΔG0T, ΔH0T, and
Glew21,22 was used. Assuming the temperature-independent ΔS0T for benzoic acid in methylbenzene + benzyl alcohol and
heat capacity change for the temperature range studied and methylbenzene + benzaldehyde binary mixtures are listed in
using the mole fraction unitary scale, one can write Tables 4 and 5. It can be found that the values of ΔH0T and
ΔG0T are positive and the value of ΔH0T increases with
ΔGθ0 ΔHθ0 ⎡ 1 1⎤ increasing temperature gradually, which indicates that the two
ln x1 = − + ⎢⎣ − ⎥⎦ dissolving processes are endothermic and not spontaneous.
Rθ R θ T
From Table 4, one can see that ΔG0T shows a gradual
ΔC p0 ⎡ θ ⎛ T ⎞⎤ increase, while ΔH0T and ΔS0T show a gradual decrease with the
+ ⎢⎣ − 1 + ln⎝⎜ ⎠⎟⎥⎦ increasing mass fraction of benzyl alcohol in methylbenzene +
R T θ (11)
benzyl alcohol solvent mixtures at constant temperature when
where R is the gas constant, T is the absolute temperature of the mass fraction of benzyl alcohol is less than 0.8. When the
the solution, and θ is the reference temperature which is chosen mass fraction of benzyl alcohol is more than 0.8, the value of
to be 273.15 K. ΔG0θ, ΔH0θ, and ΔC0pθ are the Gibbs free energy ΔG0T shows a gradual decrease, while ΔH0T and ΔS0T show a
change, dissolution enthalpy, the isobaric heat capacity at gradual increase with the increasing mass fraction of benzyl
reference temperature, respectively. alcohol. This indicates that when benzyl alcohol is added into
A comparison of eqs 9 and 11 shows that the following the solvent system (w3 is less than 0.8), less energy is required
equations can be derived: to overcome the cohesive force between the solute benzoic acid
and the solvent in the dissolving process. It causes a marked
ΔGθ0 = (Cθ − B)R − (A + C(1 + ln θ ))Rθ increase of solubility of benzoic acid with the increasing mass
ΔHθ0 = (Cθ − B)R fraction of benzyl alcohol in methylbenzene + benzyl alcohol
solvent mixtures. On the contrary, when the mass fraction of
ΔC p0 = CR benzyl alcohol is more than 0.8, the cohesive force between
benzoic acid and the solvent increases and the solubility of
ΔHθ0 − ΔGθ0 benzoic acid in the solvent mixture decreases. From Table 5,
ΔSθ0 = = (A + C(1 + ln θ ))R similar conclusions could also be obtained for the ternary
T (12)
system benzoic acid + methylbenzene + benzaldehyde. The
The dissolution enthalpy at the experiment temperature ΔH0T is value of ΔG0T increases with the increasing mass fraction of
a well-behaved function of T, so it can be calculated by the benzaldehyde when the mass fraction of benzaldehyde is less
following equation: than 0.2. However, when the mass fraction of benzaldehyde is
more than 0.2, ΔG0T shows a gradual decrease with the
ΔHT0 = ΔHθ0 + ΔC p0(T − θ ) = CRT − BR (13) increment of benzaldehyde.
H DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
4. CONCLUSIONS
By using the synthetic method, the solubilities of benzoic acid
in binary methylbenzene + benzyl alcohol solvent mixtures at
(301.05 to 355.65) K and in binary methylbenzene +
benzaldehyde solvent mixtures at (301.05 to 353.35) K were
determined at atmospheric pressure. The studied mass fractions
of benzyl alcohol and benzaldehyde in the corresponding
binary solvent mixtures range from 0.0 to 1.0. It was found that
the measured solubilities increase with the increase of
temperature at constant solvent composition.
For the ternary system benzoic acid + methylbenzene +
benzyl alcohol, the results show that the binary methylbenzene
+ benzyl alcohol solvent mixture with the mass fraction of
benzyl alcohol at 0.80 has the best dissolving capacity for
benzoic acid at constant temperature. However, for the ternary
system benzoic acid + methylbenzene + benzaldehyde, the
results show that the binary methylbenzene + benzaldehyde
solvent mixture with a mass fraction of benzaldehyde of 0.20
has the best dissolving capacity for benzoic acid at constant
temperature. The experimental data were correlated by the
nonrandom two-liquid (NRTL) equations, and the correlated
solubilities agree satisfactorily with the experimental observa-
tions.
To get the thermodynamic functions, the modified Apelblat
equation was also used to correlate the experimental
solubilities. The thermodynamic functions for the solid−liquid
equilibria system of benzoic acid in methylbenzene + benzyl
alcohol solvent mixtures and methylbenzene + benzaldehyde
solvent mixtures, including ΔG0T, ΔH0T, ΔS0T, and ΔC0p were
calculated by the Clark and Glew equation. It shows that the
dissolution process is endothermic and not spontaneous. The
obtained interaction parameters might be used in the
calculation of the solubility of benzoic acid in methylbenzene
+ benzyl alcohol and methylbenzene + benzaldehyde mixtures
as well as for the design and optimization of the related
purification process.
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: 86-731-88664151. E-mail: qinbowang@126.com.
Funding
The project is supported by Key S&T Special Project of
Zhejiang Province (2012C13007-2), the Fundamental Research
Funds for the Central Universities, and the National Nature
Science Fund (21302049).
Notes
The authors declare no competing financial interest.
■
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J DOI: 10.1021/je500775r
J. Chem. Eng. Data XXXX, XXX, XXX−XXX