J. Chem.

Thermodynamics 85 (2015) 202209

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Solubility and solution thermodynamics of sorbic acid in eight pure

organic solvents
Jing Fang a, Meijing Zhang a,b, Peipei Zhu a, Jinbo Ouyang a, Junbo Gong a,b, Wei Chen a,b,, Fengxia Xu c
a
National Engineering Research Centre of Industry Crystallization Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
b
Collaborative Innovation Centre of Chemical Science and Chemical Engineer (Tianjin), Tianjin 300072, China
c
Ecological and Environmental Monitoring Centre Sino-Sinapore Tianjin Eco-city, Tianjin 300467, China

a r t i c l e i n f o a b s t r a c t

Article history: By the gravimetric method, the solubility of sorbic acid in eight solvents including ethanol, 2-propanol,
Received 24 October 2014 methanol, 1-butanol, ethyl acetate, methyl tert-butyl ether, acetone and acetonitrile was determined
Received in revised form 31 January 2015 over a temperature range from 285.15 to K at atmospheric pressure. For the temperature range investi-
Accepted 7 February 2015
gated, the solubility of sorbic acid in the solvents increased with increasing temperature. The experimen-
Available online 14 February 2015
tal values were correlated with the linear solvation energy relationship, modied Apelblat equation, kh
equation, non-random two-liquid (NRTL) model, and Wilson model. On the other hand, the enthalpy,
Keywords:
entropy and Gibbs free energy of dissolution were obtained from these solubility values by using the
Sorbic acid
Solubility
vant Hoff and Gibbs equations. The excess enthalpy of solution was estimated on the basis of kh
Solution thermodynamics equation. Furthermore, the a priori predictive model COSMO-RS was employed to predict the solubility
Excess enthalpy of sorbic acid in selected solvents and reasonable agreement with experimental values is achieved.
COSMO-RS 2015 Elsevier Ltd. All rights reserved.

1. Introduction thermodynamic properties for the solution processes were also

(E,E)-hexa-2,4-dienoic acid (C6H8O2, sorbic acid, CAS No. 110-
44-1, gure 1) is an unsaturated fatty acid. Biological studies indi-
cate that sorbic acid can effectively inhibit the activity of mould,
yeast, aerobic bacteria and prevent the growth and reproduction
of botulism, staphylococcus, salmonella and other harmful micro-
bial [1,2]. As an internationally recognised security preservative,
sorbic acid is widely used in food, medicine, cosmetics and other
industries [3,4]. The purity of sorbic acid is critical for its further
application and can be improved by crystallization. Since the solu-
bility contributes to the choice of proper solvents [5], the method
of super saturation generation as well as the yield and productivity
of the process [6,7], the solubility of sorbic acid is a very important
parameter in the design and optimization of its crystallization pro-
cesses. However, so far there are very few studies reported on the
solubility of sorbic acid [8]. Accordingly, in this work, the solubility
of sorbic acid in eight pure solvents was measured from T = (283.15
to 323.15) K at atmospheric pressure (101.3 kPa). The
Corresponding author at: National Engineering Research Centre of Industry
Crystallization Technology, School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300072, China. Tel.: +86 22 27405754; fax: +86 22 27374971.
E-mail address: chenwei@tju.edu.cn (W. Chen).
discussed from the solubility results.
The main drawback of experimental solvent screening is that
the consumption of time and material, due to the large number
of possible solvents that could full these requirements [9]. Several
methods have been reported to predict the thermodynamic
behaviour of (solute + solvent) systems from molecular dynamics
models, quantitative (structure + property) relationship models to
classical thermodynamic models, such as NRTL, Wilson or UNIFAC
[10]. While the parameter sets of these models need to be
determined from a large amount of experimental values, a novel
model, the conductor like screening model for realistic solvation
(COSMO-RS) method was developed by Klamt over recent years
[11]. In particular, this model has a quantum chemical and
statistical thermodynamics basis with a small and general
parameter set that does not need to be adjusted for specic
compounds. Consequently, the COSMO-RS model enables efcient
prediction of a number of physicochemical properties including
solubility, activity coefcient, Henry constant and partition
coefcients etc., and yield qualitative and satisfying quantitative
predictions according to the chemical structure of compounds
[12,13]. In the present study, the COSMO-RS calculations were
carried out to evaluate the thermodynamic properties of sorbic
acid in the selected solvents.

http://dx.doi.org/10.1016/j.jct.2015.02.004
0021-9614/ 2015 Elsevier Ltd. All rights reserved.
 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209 203

2. Experimental TABLE 1
Provenance and mass fraction purity of the materials used in the experiments.

2.1. Materials Chemical Source Mass Analysis

name purity method
Sorbic acid, mass fraction purity higher than 0.998 (determined Sorbic acid Aladdin Industrial Co., Shanghai, 0.998 HPLCa
by HPLC, Agilent 1100, Agilent Technologies, USA), was purchased China
Ethanol Jiangtian Chemical Technology Co., >0.995 GCb
from the Aladdin Industrial Corporation, Shanghai, China. All the
Ltd., Tianjin, China
selected solvents including ethanol, 2-propanol, methanol, 1-bu- 2-Propanol Jiangtian Chemical Technology Co., >0.995 GCb
tanol, ethyl acetate (EA), methyl tert-butyl ether (MTBE), acetone Ltd., Tianjin, China
and acetonitrile were supplied by Tianjin Jiangtian Chemical Tech- Methanol Jiangtian Chemical Technology Co., >0.995 GCb
nology Co., Ltd., China. Values of their mass fraction purity were Ltd., Tianjin, China
1-Butanol Jiangtian Chemical Technology Co., >0.995 GCb
greater than 0.995 and were used without further purication
Ltd., Tianjin, China
(table 1). The density measurement for the solvents used in this EA Jiangtian Chemical Technology Co., >0.995 GCb
work is briey described in the Appendix, and the values are listed Ltd., Tianjin, China
in table S1 of the supporting information together with those MTBE Jiangtian Chemical Technology Co., >0.995 GCb
Ltd., Tianjin, China
reported in the literature [1419].
Acetone Jiangtian Chemical Technology Co., >0.995 GCb
Ltd., Tianjin, China
2.2. Measurements of melting properties Acetonitrile Jiangtian Chemical Technology Co., >0.995 GCb
Ltd., Tianjin, China
The melting temperature Tm and the fusion enthalpy DfusH of a
High-performance liquid chromatography.
sorbic acid were determined by differential scanning calorimetry B
Gasliquid chromatography.
(DSC 1/500, Mettler-Toledo, Switzerland). Before the analysis, the
DSC 1/500 was calibrated with indium and zinc standards. A total where m0 is the mass of the empty beaker, M1 and M2 represent the
of approximately 0.006 g of sorbic acid was added into a her- molar mass of the solute and the solvent, respectively.
metically sealed aluminium DSC pan and heated under a nitrogen After the measurement, the solid phase in equilibrium with the
atmosphere (2.5 mL  s1) from T = (293.15 to 473.15) K at a heat- saturated solution was analysed using XRPD to check for phase
ing rate of 2 K  min1. Uncertainties of the measurements were identity.
0.3 K for the temperature and no more than 3% for the enthalpy
of fusion.
2.4. X-ray powder diffraction analysis
2.3. Solubility measurement
In order to identify the solid phase in the measurement of
solubility, the X-ray powder diffraction (XRPD) was measured to
Gravimetrical method [20] was applied to determine the solubi-
characterise the solid residue. Data collection was performed on
lity of sorbic acid. A certain amount of pure solvent and an excess
Rigaku D/max-2500 (Rigaku, Japan) using Cu Ka radiation
amount of sorbic acid were added into a 100 mL jacketed glass cell
(0.071073 nm) in the 2-theta range of 2 to 50 and scanning rate
which connected to a cryo-compact circulator (CF41, Julabo,
of 0.067  s1. According to the XRPD patterns, the samples did not
Seelbach, Germany) to keep the water bath temperature at a
show any polymorphism.
constant value. A mercury thermometer with an uncertainty
within 0.05 K was inserted into the cell to monitor the real
temperature of the solution. The variation of system temperature 3. Results and discussion
for all the measurements is estimated to be within 0.05 K.
Continuous mechanical stirring ensured the adequate dissolution 3.1. Melting properties
of the solute and lasted for about 24 h to reach equilibrium.
Following stirring, the solution stood for 12 h to permit the undis- Figure 2 shows the thermal analysis (DSC) of sorbic acid. The
solved sorbic acid to settle. A total of about 3 mL of supernatant value of Tm determined in this work as the mean extrapolated
was withdrawn quickly by a syringe with a 0.2 lm PTFE lter, onset temperature (405.3 K) is in good agreement with value
and injected into a previously weighed (by an analytical balance reported by Lombardo et al. (T = 405 K) [21] and slightly less than
with 0.0001 g accuracy, Mettler Toledo ML204, Switzerland)
10 mL beaker. The total weight of the beaker and solution was
recorded immediately and denoted as m1. All samples were placed
in a vacuum drying oven at T = 313.15 K until no mass change was
observed and weighed with nal total weight m2. All experiments
were repeated three times. The estimated deviation of the
experimental solubility was less than 2%. The mole fraction
solubility x1 in pure solvent is dened as
m2  m0 =M 1
x1 ; 1
m2  m0 =M 1 m1  m2 =M2

FIGURE 1. Molecular structure of sorbic acid. FIGURE 2. DSC scan of sorbic acid.
204 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209
the value reported by Narasimhan et al. (T = 406 K) [22] and Chad-
ha et al. (T = 407.6 K, peak value) [23]. The deviations may result
from differences in equipment, samples and (or) measured condi-
tions. The fusion enthalpy DfusH of sorbic acid is determined to
be 18.76 kJ  mol1, which has not been reported so far. No evi-
dence of solid phase transformation prior to melting is observed.
The value of DfusS was calculated to be 46.28 J  K1  mol1 by
solving equation (2). The standard uncertainty for Tm is 0.3 K
and relative standard uncertainty for DfusH is 0.03:
Dfus H
Dfus S : 2
Tm
3.2. Solubility data analysis
The experimental determined solubility in the selected solvents
were plotted as x1 versus T in gure 3 and listed in table 2 together
with the calculated values by ve classical thermodynamic models.
From gure 3, it is found that the solubility in each solvent
increases with increase of temperature. Within the temperature
range from (285.15 to 323.15) K, the solubility order is
1-butanol > acetone > ethanol > MTBE > 2-propanol > methanol > EA >
acetonitrile. This sequence is not consistent with the polarity [24]
order and the Hildebrand solubility parameter (calculated by
Integrated Computer Aided System ICAS software [25,26]) order of
the solvents which is shown in table S2 of the supporting informa-
tion. To get more insight into the interactions and thermodynamic
parameters relating to the dissolution processes, a linear solvation
energy relationship had been proposed to relate chemical properties
of solute and solvent, such as polarity, ability to form hydrogen
bonds and structure to drive processes in solution: solubility,
distribution between two liquids, Gibbs free energy and enthalpy
of equilibria, wavelengths of light absorption, etc. [27]. It is custom-
ary to write any property linearly related to the Gibbs free energy of
a (solute + solvent) system as the following
XYZ XYZ0 cavity formation energy
X
solutesolvent interaction energy: 3 positive sign on the coefcient a and b indicates that HBA interaction
In the above equation, XYZ was a property linearly related to
Gibbs free energy, XYZ0 denotes a constant dependent only on
the solute. The summation of equation (3) could be extended over
all the modes of (solute + solvent) interaction. Using KamletTaft
version as follows [28]:
FIGURE 3. Plot of mole fraction solubility x1 versus T in eight solvents: (j) ethanol;
(H) 2-propanol; (D) methanol; (h) 1-butanol; (d) EA; (}) MTBE; (N) acetonitrile;
(I) acetone; , tting curve calculated by Modied Apelblat equation (equation
(A.1)).
XYZ XYZ 0 md2H pp aa bb: 4
In this equation, m, p, a and b are solvent-independent coefcients
characteristic of the process and indicative of its sensitivity to the
accompanying solvent properties. The self-cohesiveness term is
written as a product of coefcient m and the Hildebrand solubility
parameter, d2H , of the solvent. The (solute + solvent) interaction is
written in terms of non-specic (dipolarity + polarizability) interac-
tion and specic interaction, e.g. hydrogen bond donation (HBD)
and hydrogen bond acceptance (HBA). The p is polarity/polariz-
ability parameter of the solvent, a is its HBD ability, and b is its
HBA or electron pair donation ability to form a coordinated bond.
This model had been applied to obtain insights into intermolecular
interactions in solutions, e.g., ibuprofen [29] or a synthesis dye [30]
in pure and mixed solvents. The results obtained indicate that the
cohesive force of the solvents have a greater inuence on the solu-
bility of ibuprofen in pure organic solvents and the solubility
decreases as the cohesive forces increases. Values of p, a, b [27],
and d2H for the solvents in this work are listed in table S2. The results
for solubility can be represented by the following equation:
d2H
log x1 0:6444  0:5171  1:3807p 0:1034a
1000
0:6119b; 5
n 7; R2 0:88; r 0:0005:
The equation (5) is helpful to obtain information on the interac-
tions that occur in the process of solvation. As above, the polarity
parameter p has signicant weight in sorbic acid solubility while
the others also exert considerable inuence. So it is reasonable that
the solubility of sorbic acid in selected solvents does not vary along
the order of any parameter in the supporting information. The nega-
tive values of the regression coefcients of p and d2H indicate that
solubility decreases with increasing of these parameters [29]. It
means that self-cohesive interaction of solvent and dipolar
(solute + solvent) interaction leads to decreasing solubility. The
of the solvent with the carboxyl group of the solute and HBD
interaction of the solvent with the solute is favourable, but the
magnitude of the coefcients of a and b is smaller compared to those
of p and d2H indicating that solubility of the solute is less sensitive to
the variations of a and b.
In order to describe more quantitatively the (solid + liquid)
equilibrium, the solubility values and the temperature were corre-
lated by the modied Apelblat equation, kh equation, vant Hoff
equation, Wilson model and NRTL model which are presented in
the Appendix. Calculated optimised parameters of these equations
are given in tables S3 and S4 of the supporting information.For
solubility values in the eight pure solvents, the relative deviation
(RD) and average percent deviation (APD%) were used to evaluate
the accuracy of the ve correlation models above in tting the
solubility data. RD and APD% are dened as follows and are listed
in table S5 of the supporting information:
xexp
1  xcsl
1
RD exp ; 6
x1
 
 exp
N x cal 
100 X 1;i  x1;i 
APD% ; 7
N i1 xexp
1;i
where N represents the number of data points (hereinafter the
same); xexp cal
1;i and x1;i are the experimental and calculated values of
the solubility, respectively.
 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209 205

TABLE 2
Experimental and calculated mole fraction solubility of sorbic acid in pure solvents at several temperatures and p = 101.3 kPa.a

T/K 10xexp
1 10xApel
1
10xkh
1
10xvant
1 10xWilson
1
10xNRTL
1

Ethanol
285.15 0.4417 0.4407 0.4677 0.4697 0.4587 0.4157
289.15 0.4880 0.4838 0.4960 0.4980 0.4920 0.4969
293.15 0.5716 0.5706 0.5926 0.5936 0.5886 0.5500
298.15 0.6432 0.6471 0.6342 0.6352 0.6382 0.6359
303.15 0.7469 0.7483 0.7269 0.7269 0.7349 0.7657
308.15 0.8720 0.8744 0.8460 0.8460 0.8560 0.8471
312.65 1.0144 1.0159 0.9984 0.9974 1.0054 1.0302
318.15 1.2071 1.2107 1.2011 1.2001 1.2021 1.2142
323.15 1.4325 1.4030 1.4635 1.4625 1.4485 1.4037
2-Propanol
285.15 0.3833 0.3954 0.3603 0.3653 0.3623 0.3653
289.15 0.4441 0.4463 0.4351 0.4471 0.4361 0.4391
293.15 0.5300 0.5013 0.5010 0.5190 0.5060 0.5050
298.15 0.6131 0.5762 0.5711 0.6151 0.5701 0.5711
303.15 0.6836 0.6581 0.6736 0.7406 0.6716 0.6716
308.15 0.7533 0.7470 0.7653 0.7973 0.7623 0.7613
312.65 0.8597 0.8332 0.8897 0.8697 0.8867 0.8847
318.15 0.9646 0.9465 0.9796 0.9736 0.9786 0.9766
323.15 1.0340 1.0569 0.9960 1.0080 1.0020 1.0010
Methanol
285.15 0.3278 0.3502 0.2948 0.2968 0.2948 0.2948
289.15 0.3917 0.4020 0.3736 0.3747 0.3747 0.3737
293.15 0.4574 0.4588 0.4524 0.4514 0.4524 0.4504
298.15 0.5526 0.5373 0.5696 0.5656 0.5666 0.5696
303.15 0.6425 0.6245 0.6625 0.6605 0.6625 0.6745
308.15 0.7492 0.7206 0.7812 0.7782 0.7792 0.7722
312.65 0.8300 0.8148 0.8460 0.8440 0.8450 0.8550
318.15 0.9336 0.9401 0.9216 0.9216 0.9226 0.9166
323.15 1.0598 1.0637 1.0378 1.0428 1.0388 1.0328
1-Butanol
285.15 0.6187 0.6561 0.5757 0.5787 0.5757 0.5677
289.15 0.7377 0.7377 0.7357 0.7387 0.7357 0.7387
293.15 0.8437 0.8237 0.8627 0.8627 0.7617 0.8747
298.15 0.9730 0.9429 1.0050 1.0030 1.0040 1.0040
303.15 1.0791 1.0741 1.0881 1.0851 1.0881 1.0871
308.15 1.2066 1.2178 1.1996 0.1966 1.2006 1.1986
312.65 1.3536 1.3583 1.3516 1.3496 1.3526 1.3506
318.15 1.5400 1.5450 1.5340 1.5340 1.5350 1.5330
323.15 1.7338 1.7295 1.7298 1.7348 1.7298 1.7288
EA
285.15 0.2662 0.2702 0.2612 0.2622 0.2562 0.2582
289.15 0.3137 0.3157 0.3107 0.3118 0.3077 0.3097
293.15 0.3575 0.3675 0.3475 0.3478 0.3475 0.3495
298.15 0.4522 0.4412 0.4632 0.4634 0.4632 0.4632
303.15 0.5421 0.5271 0.5581 0.5575 0.5591 0.5661
308.15 0.6265 0.6255 0.6285 0.6277 0.6335 0.6325
312.65 0.7132 0.7262 0.7012 0.6999 0.7082 0.6952
318.15 0.8615 0.8675 0.8555 0.8555 0.8585 0.8585
323.15 1.0205 1.0145 1.0255 1.0266 1.0175 1.0195
MTBE
285.15 0.4026 0.3936 0.4146 0.4176 0.4167 0.4126
289.15 0.4391 0.4461 0.4331 0.4341 0.4340 0.4341
293.15 0.5119 0.5079 0.5169 0.5179 0.5175 0.5179
298.15 0.5772 0.5902 0.5612 0.5602 0.5609 0.5572
303.15 0.6931 0.6891 0.6951 0.6931 0.6940 0.7021
308.15 0.7846 0.7966 0.7676 0.7646 0.7657 0.7726
312.65 0.9299 0.9139 0.9459 0.9439 0.9443 0.9439
318.15 1.0872 1.0712 1.1062 1.1062 1.1058 1.1172
323.15 1.2125 1.2285 1.1985 1.2015 1.2003 1.1825
Acetone
285.15 0.4758 0.4658 0.4948 0.4948 0.4926 0.4738
289.15 0.5281 0.5311 0.5288 0.5311 0.5264 0.5181
293.15 0.6129 0.6099 0.6169 0.6169 0.6163 0.6029
298.15 0.7008 0.7168 0.6778 0.6788 0.6790 0.6898
303.15 0.8711 0.8521 0.8881 0.8881 0.8898 0.8991
308.15 0.9678 0.9898 0.9318 0.9328 0.9347 0.9538
312.65 1.1540 1.1500 1.1430 1.1480 1.1561 1.1640
318.15 1.3951 1.3701 1.4281 1.4281 1.4287 1.4151
323.15 1.5636 1.5806 1.5526 1.5506 1.5493 1.5406

(continued on next page)

206 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209

TABLE 2 (continued)

T/K 10xexp
1 10xApel
1
10xkh
1
10xvant
1 10xWilson
1
10xNRTL
1

Acetonitrile
285.15 0.0625 0.0657 0.0596 0.0604 0.0575 0.0579
289.15 0.0746 0.0781 0.0712 0.0718 0.0700 0.0704
293.15 0.0980 0.0926 0.1032 0.1036 0.1016 0.1016
298.15 0.1122 0.0041 0.1102 0.1102 0.1109 0.1112
303.15 0.1486 0.1398 0.1571 0.1567 0.1566 0.1563
308.15 0.1722 0.1707 0.1736 0.1728 0.1752 0.1752
312.65 0.1955 0.2034 0.1874 0.1866 0.1916 0.1920
318.15 0.2484 0.2510 0.2459 0.2456 0.2474 0.2473
323.15 0.3058 0.3025 0.3093 0.3102 0.3055 0.3049
a
Standard uncertainties are u(T) = 0.05 K, ur(x1) = 0.02 and u(p) = 0.3 kPa.

As shown in table S5, the APD% values of the three empirical TABLE 3
equations in the eight solvents are lower than those of the local Apparent standard thermodynamic properties of sorbic acid in selected solvents at
T = 302.9 K and p = 101.3 kPa.a
composition models. Moreover, the modied Apelblat equation
gave the most accurate prediction. Furthermore, it was found that Solvent DsolnG DsolnH DsolnS fH fTS
the sequence of the APD% values calculated by the same equation kJ  mol1 kJ  mol1 kJ  K1  mol1
was almost opposite of the solubility order, which indicates that Ethanol 6.471 23.56 56.43 0.580 0.420
the higher the solubility, the more accurate is the prediction. 2-Propanol 6.766 18.24 37.88 0.614 0.386
Methanol 7.018 23.37 53.97 0.588 0.412
1-Butanol 5.640 19.88 47.01 0.583 0.417
3.3. Thermodynamic properties of solution EA 7.437 26.88 64.18 0.580 0.420
MTBE 6.739 22.93 53.44 0.586 0.414
Acetone 6.21 24.61 60.73 0.572 0.428
The vant Hoff equation relates the natural logarithm of the Acetonitrile 10.77 31.27 67.68 0.604 0.396
mole fraction solubility as a linear relationship with the reciprocal a
Standard uncertainties are u(T) = 0.05 K and u(p) = 0.3 kPa.
of the absolute temperature, as drawn in gure 4. The dissolution
enthalpy DdisH and dissolution entropy DdisS can be calculated
from the slope and the intercept of the tting line, respectively. DsolnH, entropic DsolnS, Gibbs free energy DsolnG) at this
The dissolution Gibbs free energy was obtained from the following temperature are dened as apparent standard properties of the
equation [31] and is shown in table S6 of supporting information: solution, and calculated by means of the following expressions [32]:
 
Ddis G Ddis H T Ddis S: 8 @ ln x1 Dso ln H
 ; 9
@1=T  1=T hm p R
From the values given in tables S3 and S6 of the supporting
information, it is found that DdisH, DdisS and DdisG are all positive
in the eight solvents, which indicates that the dissolution processes Dso ln G R  T hm  intercept; 10
are endothermic, entropy-driven and not spontaneous. Moreover
the order of DdisG values is exactly opposite of the solubility order Dso ln H  Dso ln G
Dso ln S : 11
in these solvents. T hm
Throughout the heating process from T = (283.15 to 323.15) K in Obviously, treating ln x1 as a linear function of 1=T  1=T hm ,
this study, a mean harmonic temperature Thm [calculated by: DsolnH and DsolnG could be calculated from the slope and the
.P
N
T hm N i1 1=T] was introduced, and the Thm obtained in this
intercept of the line, respectively. Relative contributions by DsolnH
work is T = 302.9 K. The thermodynamic properties (enthalpy and DsolnS toward DsolnG were obtained by equations (12) and
(13), respectively:
jDso ln H j
fH ; 12
jDso ln H j jT hm Dso ln S j

jT hm Dso ln S j
fTS : 13
jDso ln H j jT hm Dso ln S j
The apparent standard enthalpy, entropy and Gibbs free energy
of the solution were positive in every case. Equations (12) and (13)
were used to compare the relative contribution to the standard
Gibbs free energy by enthalpy and entropy in the solution process.
The corresponding apparent standard thermodynamic properties
in all solvents and the values of fH and fTS are listed in table 3.
The values of fH are nearly 0.6, which indicates that the main con-
tributing force to the standard Gibbs free energy is the enthalpy
during the dissolution of sorbic acid in all the solvents studied [33].

3.4. Excess enthalpy of the solutions

FIGURE 4. Fitting line of vant Hoff equation in selected solvents: (j) ethanol; (H)
2-propanol; (D) methanol; (h) 1-butanol; (d) EA; (}) MTBE; (N) acetonitrile; (I) By applying the fusion enthalpy DfusH and fusion entropy DfusS
acetone. The dashed line represents the ideal solubility. obtained, the ideal solubility of sorbic acid is plotted as a dashed
 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209 207

TABLE 4
Excess enthalpy of the sorbic acid solutions studied at several temperatures and p = 101.3 kPa.a

T/K HE kJ  mol1
Ethanol 2-Propanol Methanol 1-Butanol EA MTBE Acetone Acetonitrile
285.15 0.38 1.44 0.82 0.58 0.46 0.66 0.19 0.56
289.15 0.42 1.55 0.98 0.69 0.54 0.72 0.21 0.67
293.15 0.49 1.76 1.14 0.79 0.61 0.84 0.24 0.87
298.15 0.55 2.03 1.38 0.91 0.77 0.95 0.27 1.00
303.15 0.64 2.37 1.61 1.01 0.93 1.14 0.34 1.33
308.15 0.74 2.60 1.87 1.12 1.07 1.29 0.38 1.54
312.65 0.86 2.85 2.08 1.26 1.22 1.53 0.45 1.75
318.15 1.03 3.20 2.33 1.44 1.48 1.79 0.54 2.22
323.15 1.22 3.43 2.65 1.62 1.75 2.00 0.61 2.73
a
Standard uncertainties are u(T) = 0.05 K and u(p) = 0.3 kPa.

The results could be interpreted in terms of the contribution of

several kinds of interactions in solution [37]. The enthalpy of cavity
formation (required for solute accommodating) is endothermic to
overcome the cohesive forces of the solvent and decreased solubi-
lity. On the other hand, the enthalpy of (solute + solvent) interaction
is exothermic and based mainly on van der Waals and hydrogen
bonding interactions. It is consistent with the characteristics of the
systems studied implied by equation (15). As shown in the support-
ing information, the positive values were obtained for enthalpy of
sorbic acid mixing with the selected solvents, it could indicate that
the cross associating intermolecular interactions established
between sorbic acid and these solvents are weaker than the
self-associating interactions so as to result in endothermic mixing
processes and the increasing values of HE with increasing tem-
perature. Similar behaviour is also observed for other systems [38].

3.5. Comparison of experimental and predicted solubility

Solubility predictions of sorbic acid were performed in each sol-

FIGURE 5. Comparison of predicted and experimental solubility: (a) methanol; (b)
1-butanol. (j) experimental; (N) no reference; (H) reference.
line in gure 4. This indicates that the experimental solubility val-
ues are smaller than the ideal solubility and the values of the
excess enthalpy of the solution, HE are positive in the solution sys-
tems studied [34]. The excess enthalpy of the solution HE can be
estimated from equation (14) [35,36], which might be used to
obtain a more detailed understanding of solution characteristics.
The estimated values of HE are shown in table 4 for every solution:
hR Dfus H HE =x1 ;
where x1 is the mole fraction solubility of sorbic acid in solution, h is
the parameter in the kh equation.
vent at different temperature by the quantum chemical COSMO-RS
calculation as implemented in COSMOthermX [39]. The detailed
description of the theory had been given in Appendix A and else-
where [11]. The .cosmo input les at BP-TZVP level for each com-
pound were taken from the COSMObase-1301 database. Only the
lowest energy conformations (in the conductor reference state)
were taken into account. All of the calculated values of solubility
were obtained by the iterative algorithm.
A quantitative structure property relationship (QSPR) approach
could be used to calculate a completely a priori solubility, but it
was not accurate. On the other hand, DfusG could be calculated
with accuracy as the experimental values of DfusH and Tm of sorbic
acid were known.
As a result, it was suggested that the solubility of sorbic acid
increased with increasing temperature which is consistent with
the experimental results. For solubility in all solvents studied, it
was revealed that COSMO-RS is capable of predicting the correct
temperature dependence.
To get a better prediction, the measured solubility in 1-butanol
at T = 298.15 K was taken as a reference to cancel the error in DfusG
of the solute. As a result, the predicted and experimental results
are markedly similar. Simulated values of solubility of 1-butanol
and methanol are plotted in gure 5 together with the
experimental results and the other solvents are shown in gure
S1 of the supporting information.
In order to quantify the deviation between the theoretical and
measured values intuitively, the predicted and experimental
14 solubility for all the selected solvents at all temperatures in mole
fraction log-units and additional results of the statistical analysis
are summarized in table S7 of the supporting information.
Obviously, the deviations of the predictions with a reference from
208 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209

experimental values are well below 0.4 for most of the solvents, Appendix B. Solubility models
and even 0.1 in the case of 1-butanol. In spite of the deviations
observed, it is unambiguous that the COSMO-RS model could be In this paper, we applied three empirical equations and two
used to predict solubility of sorbic acid in selected solvents. local composition models to correlate and analyse the experimen-
tal solubility.
4. Conclusions
B.1. Modied Apelblat equation
In this paper, the solubility of sorbic acid in eight pure organic sol-
vents was measured by the gravimetric method from T = (283.15 to This semi-empirical equation [41] put forward by Heidman
323.15) K. For all the selected solvents, the solubility of sorbic acid et al. can be described as
increases with increasing temperature. The linear energy relation-
ship, modied Apelblat equation, vant Hoff equation, kh equation, B
ln x1 A C ln T: B:1
Wilson model and NRTL model were used to correlate the values T
of the solubility. The solubility order of sorbic acid in selected sol-
vents is not consistent with either the order dened by the polarity B.2. kh equation
or the Hildebrnd solubility parameter (dH ). According to the linear
Gibbs free energy relationship, the solubility values are dependent Solubility data could also be calculated by the kh equation [42]
on various parameters (a, b, p) and d2H so that solubility does not which was proposed by Buchowski et al. and expressed as
vary along the order of any parameter mentioned above. The modi-     
1  x1 1 1
ed Apelblat equation gave the most satised correlation with solu- ln 1 k kh  : B:2
bility results. In addition, based on the vant Hoff equation, the
x1 T Tm
dissolution thermodynamic properties including enthalpy DdisH, In the above equation, k and h are equation parameters. The val-
entropy DdisS and Gibbs free energy DdisG of sorbic acid in selected ue of k reects the non-ideality of the solution system and h repre-
solvents were calculated to be all positive values in the cases stud- sents the enthalpy of the solution [43,44].
ied. The results indicate that the dissolution processes in all selected
solvents are endothermic, entropy-driven and not spontaneous. The B.3. vant Hoff equation
values of excess enthalpy HE were derived from the kh equation. The
positive HE values of sorbic acid in the selected solvents indicate that For real solutions, the mixing effects between the solvent and
the intermolecular interactions of (solute + solvent) are weaker than solute cannot be ignored in the dissolution process. The vant Hoff
those of (solute + solute) and (solvent + solvent). This result is con- equation [45] reects the thermal effect during mixing is described
sistent with the result from tting by linear Gibbs free energy rela- as following
tionship. The COSMO-RS predictions of the solubility values of
sorbic acid in the eight solvents are in good agreement with the ln x1 Ddis H=RT Ddis S=R; B:3
measured values. The accuracy of the COSMO-RS prediction could
be further promoted by taking the experiment values in 1-butanol where DdisH and DdisS are the dissolution enthalpy and entropy,
at T = 298.15 K as a reference. respectively, and R is the gas constant.

Acknowledgements B.4. Wilson model

The authors are grateful to Prof. Raqul Gani for providing the In a binary system that consists of solute 1 and solvent 2, the
software ICAS. This work is nancial supported from National Nat- Wilson model can be expressed as follows [46]:
ural Science Foundation of China China (NNSFC 21376164 and  
K12 K21
21376165), National High Technology Research and Development ln c1  lnx1 K12 x2 x2  ; B:4
x1 K12 x2 x2 K21 x1
Program (863 program) China (2012AA021202) and Open Project
of the Key Laboratory of Advanced Energy Materials Chemistry of V2
the Ministry of Education (Nankai University) China (KLAEMC- where K12 expk12  k11 =RT; B:5
V1
OP201201).
V1
K21 expk21  k22 =RT; B:6
Appendix A. Density measurement V2
K12 and K21 are Wilson parameters, V 1 and V 2 are the molar vol-
The densities of the solvents in this work were determined by a
umes of the solute and the solvent, respectively. Dk12 k12  k11
pycnometer with a bulb volume of 25 mL and an analytical balance
and Dk21 k21  k22 are the cross interaction energy parameters.
(Mettler Toledo ML204, Switzerland). All the experiments were tak-
en at T = 298.15 K and 101.3 kPa in a controlled-temperature
B.5. NRTL model
laboratory. First, the mass of the empty pycnometer was deter-
mined by the balance and denoted as w. Then 25 mL of distilled
In a binary system, the activity coefcient of NRTL model is
water were added into the pycnometer to determine the total
calculated by [47]
weight W. Lastly, the pycnometer was dried in a vacuum oven " #
and then lled with 25 mL of the given solvent. The total mass s21 G221 s12 G12
was denoted as W0 . The density of the solvent was calculated by [40] ln c1 x22 : B:7
x1 x2 G21 2 x2 x1 G12 2
W0  w
q qcal ; A:1 In the above equation
W w
G12 expa12 s12 ; B:8
where qcal is the density of the calibration liquid. In our work, it
represents the density of the distilled water with the value of
G21 expa12 s21 ; B:9
0.997 g  cm3 [17].
 J. Fang et al. / J. Chem. Thermodynamics 85 (2015) 202209 209

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Appendix D. Supplementary data

Supplementary data associated with this article can be found, in

the online version, at http://dx.doi.org/10.1016/j.jct.2015.02.004. JCT 14-595