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