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Thermodynamic Models For Determination of The Solubility of F2C
Thermodynamic Models For Determination of The Solubility of F2C
a r t i c l e i n f o a b s t r a c t
0378-3812/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2014.01.039
58 T. Prapasawat et al. / Fluid Phase Equilibria 367 (2014) 57–62
O 320.0
O O 280.0
240.0
Solubility (g/L)
200.0
160.0
Fig. 1. Chemical structure of 2,5-bis(2-furylmethylidene) cyclopentan-1-one.
120.0
2. Experimental 80.0
40.0
2,5-Bis(2-furylmethylidene)cyclopentan-1-one (structure
0.0
shown in Fig. 1) was prepared by aldol condensation of fur- 293.15 313.15 333.15 353.15 373.15 393.15 413.15
fural with cyclopentanone in aqueous solution according to the T/K
literature [19]. Analytical grade methanol (99.8% wt) and tetrahy-
drofuran (THF, 99.5% wt) were supplied by Centralchem® (Slovak Fig. 3. Solubility of F2 C in different solvents at temperatures from 308.15 to
Republic). Re-distilled water was used for the experiments. The 403.15 K; ( ) tetrahydrofuran, () water-tetrahydrofuran (1:1 vol.), () methanol
properties of these solvents are presented in Table 1. and (䊉) water.
m1 /M1
xi = (1)
m1 /M1 + m2 /M2 + m3 /M3
Table 1
Properties of solvents.
Solvents Properties
3.2. Thermodynamic models of various organic compounds [8,21]. The polynomial empirical
equation can be easily applied for correlating the solubility data
The correlation between temperature and solubility of F2 C in [12,21]. The correlation of solubility with the polynomial empirical
different solvents can be explained by thermodynamic models, equation is based on the assumptions described by Zhang et al.
e.g. by the polynomial empirical equation, the Van’t Hoff, and the [12] as shown in Eq. (2).
modified Apelblat models. These equations are widely used to The polynomial equation was used to identify the solubility of
describe the solubility behavior of solute for not only ideal but F2 C in different solvents. The correlation is displayed in Fig. 4 and
also non-ideal solutions. In addition, the selected thermodynamic the parameters are listed in Table 3.
models can describe the influence of temperature on the solubility
xi = A + BT + CT 2 + DT 3 + . . . + ˛T n ; n≥1 (2)
20.0
(d) Water
353.15 0.007 0.763 0.107 0.279 0.0
363.15 0.012 0.094 0.130 0.168 293.15 313.15 333.15 353.15 373.15 393.15 413.15
373.15 0.020 0.173 0.164 0.166
T/K
383.15 0.038 0.102 0.003 0.048
393.15 0.062 0.072 0.077 0.253
Fig. 4. Correlation of the mole fraction of solubility of F2 C in different solvents at
398.15 0.081 0.062 0.015 0.236
temperatures from 308.15 to 403.15 K using the polynomial empirical equation;
403.15 0.111 0.095 0.002 0.127
( ) tetrahydrofuran, () water–tetrahydrofuran (1:1, v/v), () methanol and (䊉)
a
Standard uncertainties u are u(t) = ±0.1 K, ur (xi ) = ±0.007. water. Dashed lines calculated from the model.
60 T. Prapasawat et al. / Fluid Phase Equilibria 367 (2014) 57–62
Table 3
Parameters of the polynomial empirical equation for F2 C solubility in different solvents at temperatures from 308.15 to 403.15 K.a
180.0 180.0
160.0 160.0
140.0 140.0
120.0
120.0
100.0
10 x i
100.0
10 x i
3
80.0
3
80.0
60.0
60.0
40.0
40.0
20.0
20.0
0.0
0.0 293.15 313.15 333.15 353.15 373.15 393.15 413.15
293.15 313.15 333.15 353.15 373.15 393.15 413.15 T /K
T/ K
Fig. 6. Correlation of mole fractions of solubility of F2 C in different solvents at
Fig. 5. Correlation of mole fractions of solubility of F2 C in different solvents at tem-
temperatures from 308.15 to 403.15 K using the modified Apelblat model; ( )
peratures from 308.15 to 403.15 K using the Van’t Hoff model; ( ) tetrahydrofuran, tetrahydrofuran, () water–tetrahydrofuran (1:1, v/v), () methanol and (䊉) water.
() water–tetrahydrofuran (1:1, v/v), () methanol and (䊉) water. Dashed lines Dashed lines calculated from the model.
calculated from the model.
model. As is seen from Fig. 5, the calculated data are in accordance 3.3. Thermodynamic parameters
with the experimental data with R2 > 0.9824. The parameters from
the regression are shown in Table 4. Thermodynamic parameters of F2 C solute relating to the mole
The modified Apelblat model (Eq. (7)) which is a semi-empirical fraction of solubility at the corresponding temperatures were esti-
model obtained from the Clausius–Clapeyron equation was mostly mated. In previous studies, the Van’t Hoff equation expressing the
adopted to describe the thermodynamic solubility of polar and non logarithm of the mole fraction of a solute vs. reciprocal temperature
polar solutions [5,7,10,21]. (1/T) was employed to evaluate the values defined in Eq. (8). The
o ) can be obtained
B standard molar enthalpy of dissolution (HDiss
ln xi = A + + C ln T (7)
T from the slope of this equation in the so-called Van’t Hoff plot
where xi and T are the mole fraction of F2 C and absolute tempera- [5,7,20,22,23].
ture (K), respectively, and A, B and C are model parameters which ∂ ln xi
o
are obtained from the regression curve as shown in Table 5. The HDiss = −R · (8)
∂(1/T )
correlative data between experimental data and modified Apelblat
model are illustrated in Fig. 6. where R represents the gas constant (8.314 J mol−1 K−1 ), xi is the
According to the above mentioned correlations of experimen- mole fraction of F2 C at system temperature and T is the correspond-
tal data obtained at different temperatures in various solvents ing absolute temperature of solution (K).
Table 5
Parameters of the modified Apelblat model for F2 C solubility in different solvents at temperatures from 308.15 to 403.15 K.a
Table 6
Thermodynamic parameters of dissolution of F2 C in different solvents at mean temperatures.a
6.00 that the solubility strongly depends on the temperature [7,17]. The
positive standard molar entropy of dissolution means that in each
4.00 solvent the entropy is the driving force of the dissolution process
[7]. In addition, the standard molar Gibbs energy for all solvents is
2.00 negative except water. The negative value of the standard molar
Gibbs energy indicates that the dissolution process is spontaneous.
10 ln xi
Tmean mean temperature of the experiment [7] K. Wang, Y.H. Hu, W.G. Yang, S. Guo, Ying Shi, J. Chem. Thermodyn. 55 (2012)
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