Solubility and Dissolution Thermodynamics for 1,3,5-Trichlorobenzene

Dec 8, 2015 - 1,3,5-Trichlorobenzene is a very useful chemical in plant protection, for instance in ... The temperature was controlled by a smart ther...
3 downloads 0 Views 572KB Size
Download PDF
Article pubs.acs.org/jced

Solubility and Dissolution Thermodynamics for 1,3,5Trichlorobenzene in Organic Solvents Rongrong Li,*,† Jian Wang,‡ Renjie Xu,‡ Cunbin Du,‡ Shuo Han,‡ Long Meng,‡ and Hongkun Zhao‡ †

Institute of Applied Chemistry, TaiZhou University, Linhai, Zhejiang 317000, P. R. China College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, P. R. China

‡

ABSTRACT: The solubility of 1,3,5-trichlorobenzene in n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexane, toluene, ethyl acetate, and acetone were obtained experimentally in temperatures ranging from (273.15/280.65 to 308.15) K under a pressure of 0.1 MPa with a chromatographic method. The solubility data of 1,3,5-trichlorobenzene in those selected organic solvents increased with increasing temperature. The order of the solubility data values is as follows: toluene > cyclohexane > ethyl acetate > (n-butanol, acetone) > isobutyl alcohol > n-propanol > isopropyl alcohol. The obtained solubility data of 1,3,5-trichlorobenzene in the studied solvents were correlated by using modified Apelblat equation, λh equation, Wilson model, and NRTL model. The four models all provide acceptable results for the system of 1,3,5trichlorobenzene in the selected solvents. Furthermore, the thermodynamic properties of solution, including molar dissolution enthalpy (ΔsolH0) and the excess enthalpy for 1,3,5-trichlorobenzene in eight pure solvents, were obtained.

■

INTRODUCTION 1,3,5-Trichlorobenzene is a very useful chemical in plant protection, for instance in synthesizing the plant protecting agent trichloro-trinitrobenzene.1−3 It is also an important raw material in the preparation of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB).4 Many synthetic methods of 1,3,5-trichlorobenzene have been reported in the publications. 1,2,4Trichlorobenzene can be converted into 1,3,5-trichlorobenzene by isomerization with Friedel−Crafts catalysts and cocatalysts.5−7 1,3,5-Trichlorobenzene can also be produced from 2,4,6-Cl3C6H2NHNH2 upon oxidation with alkaline KMnO4 or Fehling solution, during which a maroon colored compound (insoluble in ethanol and a having a mp of 135−136 °C) also appears together with 1,3,5-trichlorobenzene (soluble in ethanol) using 2,4,6-trichloroaniline, HCl/NaNO2 and ethanol.7,8 Mehilal and Agrawal modified the route using H2SO4/ NaNO2 and H3PO2.4 In recent years other ways were proposed to prepare 1,3,5-trichlorobenzene, for example, substituting nitro groups with chlorine in the absence of catalyst, during which the nitro groups of raw materials are replaced completely by chlorine in a mild manner,9 or using water as raw material.10 During the production process of 1,3,5-trichlorobenzene, the isomers (e.g., 1,2,4-trichlorobenzene) exist in the product. As a result, 1,3,5-trichlorobenzene must be separated from its isomeric mixture before use. In previous publications, the 1,3,5-trichlorobenzene was separated from its isomer mixture by adsorption by using faujasite type zeolite as an adsorbent and xylene as a desorbing agent.11 However, this separation method is very complicated. Crystallization is an effective method to purify 1,3,5-trichlorobenzene. The fundamentals for solvent crystallization are solubility of 1,3,5-trichlorobenzene in solvents and dissolution thermodynamic properties, which can optimize the basic design of crystallization process and increase © 2015 American Chemical Society

the purity and yield of 1,3,5-trichlorobenzene. So it is of importance to obtain the solubility of 1,3,5-trichlorobenzene in various solvents and the thermodynamic properties of solutions of 1,3,5-trichlorobenzene in advance. The solubility data of 1,3,5-trichlorobenzene in water were determined;12,13 however, the solubility data in pure organic solvents, to the best of the authors’ present knowledge, are very scare in the literature. To enrich and provide the detailed solubility data for engineering purposes, the solubility of 1,3,5-trichlorobenzene in the solvents of n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexane, toluene, ethyl acetate, and acetone were determined at temperatures ranging from (273.15/280.65 and 313.15) K under 0.1 MPa. The temperature range should be as wide as possible. However, the melting points of 1,3,5trichlorobenzene and cyclohexane are about 336 and 279.5 K, respectively, so the experimental temperature was selected in the range from (273.15 to 313.15) K except for cyclohexane (280.65 to 313.15) K. The aim of the present paper is to (1) measure the solubility data of 1,3,5-trichlorobenzene in eight pure organic solvents, (2) correlate the solubility data with the Apelblat equation, λh equation, Wilson model, and NRTL model, and (3) evaluate the dissolution properties of 1,3,5-trichlorobenzene.

■

EXPERIMENTAL SECTION Materials and Apparatus. 1,3,5-Trichlorobenzene was provide by Shanghai Ziyi Reagent Factory, China. It was purified by recrystallization three times in acetone. The final content of 1,3,5-trichlorobenzene was 0.997 in mass fraction, Received: July 16, 2015 Accepted: November 25, 2015 Published: December 8, 2015 380

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 1. Source and Purity of the Materials Used in This Work molar mass

chemicals 1,3,5-trichlorobenzene n-propanol isopropyl alcohol n-butanol isobutyl alcohol cyclohexane toluene ethyl acetate acetone a

−1

g·mol

181.45

melting point

K 335.9a 336.7b

melting molar enthalpy −1

kJ·mol

17.56a 18.2b

density

kg·m

−3

1220.4c

60.01 60.06 74.12 74.12 84.16 92.14 88.11 58.08

purification method

mass fraction purity

analysis methodd

Shanghai Ziyi Reagent Factory

crystallization

0.997

GC

Sinopharm Chemical Reagent Co., Ltd., China

none none none none none none none none

0.994 0.996 0.997 0.996 0.995 0.995 0.997 0.996

GC GC GC GC GC GC GC GC

molar volume

75.14 76.92 91.97 92.91 108.57 106.85 98.5 73.4

source

Taken from ref 26. bTaken from ref 27. cTaken from ref 28. dGas chromatography.

Analysis. In this work, the gas chromatograph (GC), type Agilent 7890A, was used to determine the composition of the equilibrium liquid phase. The GC apparatus was equipped with a 30 m × 0.32 mm × 0.25 μm capillary column (model: DB1701) and a flame ionization detector. The carrier gas was nitrogen with a velocity of 10 mL·min−1. The temperature of the injection chamber was set to 573 K, and the detector temperature was set to 510 K. The GC internal standard method was employed in the solubility measurement of 1,3,5trichlorobenzene in pure organic solvents. A series of solutions with a certain composition of 1,3,5-trichlorobenzene were prepared before experiment, and 20 μL of the solution was taken out to mensurate with the GC. The dependence of peak area on the composition of 1,3,5-trichlorobenzene was obtained and was employed to evaluate the solubility of samples. To reduce the deviations, each analysis was carried out three times, and the average value of the three analyses was considered as the final one. The relative standard uncertainty of the solubility is estimated to be 2.0% in mole fraction. The solubility of 1,3,5-trichlorobenzene in mole fraction in the pure solvents is calculated using eq 1:

which was determined by means of a gas chromatography (Agilent 7890A Infinity GC, Agilent Technologies). The solvents with analytical grade, including n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexane, toluene, ethyl acetate and acetone were all provided from Sinopharm Chemical Reagent Co., Ltd., China, and used in experiment with no further purification. The detail information for 1,3,5trichlorobenzene and all solvents were presented in Table 1. The temperature was controlled by a smart thermostatic water bath (model: DZKW-4) purchased from Ningbo Scientz Biotechnology Co., Ltd. An analytical balance with a precision of 0.0001 g was used to determine the mass of the solute, solvent, and saturated solution. Solubility Determination. In the experiment, the solubility data of 1,3,5-trichlorobenzene in various solvents were measured by using the chromatographic method, which was widely used in solubility determination in the literature.14−16 An excessive amount of 1,3,5-trichlorobenzene was added to an Erlenmeyer flask filled with 50 mL of solvent. The flask was equipped with an electromagnetic agitation. The temperature of the mixture was kept constant by water circulation from the thermostatic water bath by means of the jacket. The actual temperature was shown by a thermometer inserted into the flask. To prevent the solvent from escaping, a condenser was attached to the Erlenmeyer flask. The mixture was stirred continuously for 20 h with the magnetic agitator. To confirm the equilibrium time of the mixture, the liquid phase was extracted out every 1 h with a 0.2 μm pore syringe filter and then measured by GC. The mixture was assumed to be in equilibrium if the two analytical results were the same. The results suggested that the system reached equilibrium 16 h later. As a result, in the present work, all samples were equilibrated for least for 24 h. After this time the stirring was stopped. Thirty minutes later, the entire solid precipitated out of solution. Two mL of the upper liquid phase was extracted out with a 5 mL syringe preheated in the water bath. Subsequently the extracted liquid phase was transferred quickly into a preweighed volumetric flask of 25 mL. The volumetric flask was sealed quickly to prevent the solvent from escaping. The mass of the sample was weighed with the analytical balance, and then diluted using the same solvent. Twenty μL of the liquor was taken out to be analyzed by means of gas chromatography (GC).

x=

m1/M1 m1/M1 + m2 /M 2

(1)

where M 1 and M2 denote the molar mass of 1,3,5trichlorobenzene and solvent, respectively, and m1 and m2 denote the corresponding mass.

■

RESULTS AND DISCUSSION Solubility Data. The mole fraction solubility data of 1,3,5trichlorobenzene in n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, cyclohexane, toluene, ethyl acetate, and acetone at the temperatures ranging from (273.15/280.65 to 308.15) K are listed in Table 2 and plotted in Figures 1 and 2. Furthermore, the Van’t Hoff plots of ln(x) versus 1/T in various solvents were graphically shown in Figure 3. Figures 1 and 2 show that with the increase in temperature, the solubility of 1,3,5-trichlorobenzene in various organic solvents increases. At the same temperature, the solubility values of 1,3,5trichlorobenzene in isopropyl alcohol are lower than those in other solvents, and cyclohexane demonstrates the strongest positive dependency on temperature. The solubility values are larger in toluene than in the other solvents at the same temperature. It can also be seen from Figures 1 and 2 that the 381

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 2. Experimental Mole Fraction Solubility (x) of 1,3,5-Trichlorobenzene in Different Solvents together with the Relative Deviation and Relative Average Deviation at the Temperature Range from T = (273.15 to 313.15) K under 0.1 MPaa 100RD T/K

x

Apelblat equation

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RADb

0.02106 0.02376 0.02732 0.03129 0.03588 0.04059 0.04658 0.05322 0.05979 0.06767 0.07641 0.08535 0.09729 0.1086 0.1216 0.1379 0.1576

−1.30 −2.36 −1.39 −0.73 0.13 −0.26 0.85 1.62 0.80 0.80 0.65 −0.50 0.46 −0.63 −1.28 −0.58 0.99 0.90

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.01438 0.01669 0.01949 0.02247 0.02561 0.0297 0.03392 0.03845 0.0441 0.05091 0.05797 0.06486 0.07401 0.08487 0.09685 0.1097 0.1265

−3.51 −2.27 −0.38 0.24 −0.23 1.07 0.90 0.03 0.38 1.41 1.14 −0.84 −0.81 −0.24 −0.10 −0.66 0.64 0.88

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.03600 0.04065 0.04671 0.05292 0.05916 0.06795 0.07673 0.08524 0.09694 0.1067 0.1221 0.1355 0.1499 0.1655 0.1855 0.2072 0.2334

−1.37 −1.80 −0.30 −0.09 −1.08 0.80 1.10 −0.09 1.19 −0.63 1.51 0.74 −0.26 −1.31 −0.78 −0.40 0.88 0.84

λh equation

NRTL model

Wilson model

0.66 −0.96 −0.49 −0.23 0.30 −0.35 0.58 1.22 0.33 0.31 0.19 −0.88 0.20 −0.75 −1.23 −0.35 1.40 0.61

−0.72 −1.82 −0.85 −0.18 0.72 0.37 1.51 2.29 1.46 1.40 1.13 −0.21 0.45 −1.07 −2.31 −2.38 −1.80 1.22

−0.95 −0.54 0.67 0.76 −0.13 0.87 0.48 −0.52 −0.23 0.83 0.62 −1.25 −1.06 −0.30 0.02 −0.36 1.06 0.63

−2.10 −1.23 0.38 0.82 0.22 1.45 1.25 0.37 0.70 1.72 1.39 −0.7 −0.86 −0.58 −0.88 −2.09 −1.64 1.08

−0.02 −0.80 0.36 0.30 −0.92 0.76 0.91 −0.39 0.83 −1.02 1.15 0.43 −0.48 −1.41 −0.74 −0.21 1.21 0.70

−1.32 −1.60 0.03 0.36 −0.51 1.43 1.78 0.61 1.85 −0.03 1.96 0.99 −0.29 −1.73 −1.70 −1.95 −1.44 1.15

n-Propanol −2.14 −2.81 −1.42 −0.36 0.88 0.82 2.21 3.16 2.46 2.43 2.11 0.61 0.96 −1.01 −2.89 −3.84 −4.35 2.03 Isopropyl Alcohol −3.38 −2.14 −0.18 0.58 0.29 1.79 1.82 1.13 1.60 2.66 2.31 0.12 −0.29 −0.41 −1.30 −3.32 −3.93 1.60 n-Butanol −2.80 −2.60 −0.52 0.22 −0.30 1.94 2.52 1.54 2.87 1.02 2.91 1.75 0.15 −1.75 −2.36 −3.44 −3.96 1.92

382

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 2. continued 100RD T/K

x

λh equation

Apelblat equation

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.02462 0.02803 0.03214 0.03674 0.04203 0.04782 0.05448 0.06157 0.07079 0.08045 0.09098 0.1023 0.1170 0.1306 0.1471 0.1664 0.1906

−0.54 −0.94 −0.52 −0.32 0.04 −0.05 0.08 −0.52 0.69 0.83 0.56 −0.17 0.82 −0.49 −0.87 −0.7 0.78 0.52

280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.1309 0.1469 0.1652 0.1856 0.2073 0.2305 0.2550 0.2860 0.3181 0.3502 0.3905 0.4341 0.4807 0.5285

−0.46 −0.43 0.01 0.43 0.46 0.11 −0.59 0.18 0.23 −0.62 −0.07 0.24 0.33 −0.22 0.36

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.1687 0.1845 0.1992 0.2184 0.2399 0.2601 0.2866 0.3107 0.3372 0.3683 0.3993 0.4272 0.4627 0.5001 0.5386 0.5749 0.6187

1.50 0.94 −0.75 −0.70 −0.26 −0.94 0.15 −0.18 −0.27 0.46 0.62 −0.41 −0.04 0.25 0.34 −0.34 −0.05 0.48

273.15 275.65 278.15 280.65

0.09284 0.1015 0.1125 0.1234

0.06 −0.88 −0.24 −0.44

Isobutyl Alcohol −1.26 −1.45 −0.78 −0.31 0.33 0.51 0.89 0.50 1.84 2.03 1.70 0.78 1.39 −0.52 −1.76 −2.79 −2.86 1.28 Cyclohexane −0.26 −0.96 −1.09 −1.09 −1.32 −1.78 −2.44 −1.43 −0.99 −1.28 0.002 1.21 2.35 3.04 1.53 Toluene 2.66 1.67 −0.40 −0.69 −0.53 −1.44 −0.51 −0.96 −1.08 −0.32 −0.06 −0.91 −0.29 0.32 0.83 0.64 1.48 0.87 Ethyl Acetate −1.78 −2.00 −0.71 −0.35 383

NRTL model

Wilson model

0.36 −0.31 −0.12 −0.11 0.10 −0.10 −0.05 −0.69 0.51 0.65 0.40 −0.28 0.76 −0.50 −0.83 −0.63 0.83 0.43

−0.06 −0.61 −0.30 −0.16 0.19 0.10 0.25 −0.30 0.94 1.09 0.82 0.05 0.94 −0.55 −1.20 −1.43 −0.50 0.56

−0.31 −0.25 0.20 0.59 0.56 0.13 −0.67 −0.003 −0.04 −0.93 −0.35 0.10 0.48 0.44 0.39

−0.53 −1.33 −1.53 −1.57 −1.82 −2.25 −2.83 −1.69 −1.06 −1.1 0.50 2.08 3.67 4.86 1.96

−0.10 0.36 −0.61 −0.12 0.50 −0.19 0.73 0.13 −0.26 0.20 0.14 −0.99 −0.60 −0.14 0.27 0.06 0.94 0.37

3.43 2.10 −0.27 −0.84 −0.91 −1.99 −1.17 −1.67 −1.79 −0.94 −0.54 −1.18 −0.29 0.65 1.54 1.80 3.11 1.42

0.40 −0.67 −0.14 −0.42

−0.14 −0.98 −0.26 −0.38

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 2. continued 100RD T/K

x

λh equation

Apelblat equation

NRTL model

Wilson model

1.07 1.84 1.42 1.59 1.02 1.04 1.66 0.67 −0.09 −0.68 −0.95 −2.03 −3.59 1.32

0.47 0.82 0.10 0.10 −0.50 −0.39 0.49 −0.11 −0.34 −0.23 0.34 0.24 −0.18 0.35

0.65 1.10 0.45 0.48 −0.13 −0.05 0.74 0.03 −0.34 −0.4 −0.01 −0.30 −0.89 0.43

−3.65 −1.32 −0.48 0.20 0.78 2.10 1.99 2.50 2.15 1.97 0.68 1.07 −0.79 −2.31 −2.31 −2.27 −3.45 1.77

−1.25 0.12 0.15 0.12 0.11 0.97 0.50 0.81 0.38 0.29 −0.76 0.08 −1.14 −1.78 −0.66 0.76 1.27 0.66

−1.89 −0.25 −0.003 0.17 0.32 1.30 0.93 1.29 0.88 0.75 −0.38 0.33 −1.08 −1.97 −1.15 −0.10 −0.02 0.75

Ethyl Acetate 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.1370 0.1508 0.1641 0.1795 0.1948 0.2128 0.2338 0.2527 0.2741 0.2978 0.3249 0.3519 0.3798

0.52 0.92 0.23 0.23 −0.39 −0.30 0.53 −0.13 −0.40 −0.33 0.25 0.21 −0.06 0.36

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 100RAD

0.04189 0.0472 0.05241 0.0581 0.06435 0.07183 0.07905 0.0876 0.0963 0.1062 0.1159 0.1288 0.1403 0.1537 0.1714 0.1919 0.2131

−3.77 −1.46 −0.71 −0.16 0.26 1.42 1.16 1.55 1.13 0.97 −0.22 0.44 −0.99 −1.85 −0.92 0.37 0.84 1.07

Acetone

a

Standard uncertainty u is u(T) = 0.02 K; the relative standard uncertainty ur is ur(p) = 0.05, ur(x) = 2.0%. bRAD = (1/N)∑(|xci − xi|/xi).

Figure 1. Mole fraction solubility x of 1,3,5-trichlorobenzene in pure solvents: ■, n-propanol; ●, isopropyl alcohol; ▲, n-butanol; ▼, isobutyl alcohol. Solid line, calculated from the modified Apelblat equation.

Figure 2. Mole fraction solubility x of 1,3,5-trichlorobenzene in pure solvents: ■, cyclohexane; ●, toluene; ▲, ethyl acetate; ▼, acetone. Solid line, calculated from the modified Apelblat equation.

solubility of 1,3,5-trichlorobenzene in n-butanol, the increments of solubility values are larger in n-butanol than in acetone. So the solubility of 1,3,5-trichlorobenzene is greater in n-butanol than in acetone when the temperature is above 293.15 K. To illustrate the difference of solubility of 1,3,5-trichlorobenzene in different organic solvents, Table 3 presents the polarities, dipole moments (μ), dielectric constants (ε), and

solubility values accord to the order: toluene > cyclohexane > ethyl acetate > (n-butanol, acetone) > isobutyl alcohol > npropanol > isopropyl alcohol. For n-butanol and acetone, when the temperature is below 293.15 K, the solubility of 1,3,5trichlorobenzene is greater in acetone than in n-butanol. Owing to stronger positive dependency on temperature for the 384

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

equilibrium.16,20,23 In this work, the λh equation was used to correlate the solubility data of 1,3,5-trichlorobenzene in eight selected pure solvents. The λh equation is described as eq 3: ⎡ 1 ⎛ λ(1 − x) ⎞ 1 ⎤ ⎟ = λh⎢ − ln⎜1 + ⎥ ⎝ ⎠ x Tm/K ⎦ ⎣ T /K

where Tm is melting point of a solid under normal pressure; λ and h are the two adjustable parameters. The λ value relates to the approximate average association number of solute molecules, which shows the nonideality of a solution; the value of h stands for the enthalpy of solution. Wilson Equation. According to thermodynamic theory, the condition of liquid−solid phase equilibrium is that, at certain temperature and pressure, the fugacity of liquid phase is identical to that of solid phase.24 This condition is expressed as

Figure 3. Van’t Hoff plots of ln(x) versus 1/T in different solvents: ■, n-propanol; ●, isopropyl alcohol; ▲, n-butanol; ▼, isobutyl alcohol; ⧫, cyclohexane; +, toluene; ★, ethyl acetate; ⊕, acetone.

Table 3. Physical Properties for the Selected Solventsa

a

solvent

polarity

μ

ε (293.15 K)

δH

n-propanol isopropyl alcohol n-butanol isobutyl alcohol cyclohexane toluene ethyl acetate acetone

61.7 54.6 60.2 55.5 0.6 9.9 23 35.5

1.7 1.66 1.66 1.7 0.3 0.4 1.7 2.9

20.1 18.3 18.2 17.7 2.01 2.38 6.02 20.6

11.9 11.5 11.4 10.7 8.2 8.9 9.1 10.0

(3)

x iLγiLfiL = x isγisf is

(4)

Here s and L denote the solid state and liquid state, respectively, f i denotes the fugacity of component i, and γ denotes the activity coefficient. On the basis of the theory of liquid−solid phase equilibrium, the relationship between solubility and temperature can be deduced and expressed as25 ΔfusH ⎛ 1 1⎞ − ⎟ ⎜ R ⎝ Tm T⎠

ln(x i·γi) =

Taken from ref 17.

(5)

The activity coefficient of component i in the liquid phase can be calculated by the Wilson equation, which is expressed as eq 6 for the binary system:21

Hildebrand solubility parameters (δH) of the solvents used in this study, whose values are taken from the reference.17 It can be seen from Table 3 and Figures 1 and 2 that the sequence of the solubility from low to high is in accord with the three properties, polarity, dielectric constants (ε), and Hildebrand solubility parameters (δH) of the selected solvent with the exception of toluene, n-butanol, and isopropyl alcohol. Besides, for the systems of 1,3,5-trichlorobenzene in toluene, n-butanol, and isopropyl alcohol, the sequence of the solubility is in accordance with the dipole moment, dielectric constants (ε), and Hildebrand solubility parameter. The results indicate that the properties of solvents are significant factors to affect the solubility of 1,3,5-trichlorobenzene. Solubility Correlation. In the present work, the solubility data of 1,3,5-trichlorobenzene in eight pure solvents were correlated with four models, which corresponded to Apelblat equation,18,19 λh equation,20 Wilson model,21 and NRTL model.22 Apelblat Equation. The experimental solubility data of 1,3,5-trichlorobenzene in the studied solvents within the temperatures T = (273.15/280.65 to 313.15) K were correlated using the Apelblat equation,18,19 which was widely used in the solubility correlation. B ln x = A + + C ln T (2) T Here A, B, and C are parameters. T is the absolute temperature in Kelvin, and x is solubility of 1,3,5-trichlorobenzene in mole fraction in eight organic solvents at temperature T. λh Equation. The λh equation put forward by Buchowski and co-workers is also a semiempirical equation. It contains two adjustable parameters (λ and h) and is widely applied to correlate the solubility for systems of liquid−solid phase

⎤ ⎡ Λ12 Λ 21 ln γ1 = −ln(x1 + Λ12x 2) + x 2⎢ − ⎥ x 2 + Λ 21x1 ⎦ ⎣ x1 + Λ12x 2 (6)

Λ12 =

⎡ ⎛ V2 b ⎞⎤ exp⎢ −⎜a1 + 1 ⎟⎥ ⎣ ⎝ V1 T ⎠⎦

(7)

Λ 21 =

⎡ ⎛ V1 b ⎞⎤ exp⎢ −⎜a 2 + 2 ⎟⎥ ⎣ ⎝ V2 T ⎠⎦

(8)

In eqs 6 to 8, V denotes the molar volume. ai and bi are adjustable energy interaction parameters, which are independent of temperature and may be acquired by means of regression of the solubility data. NRTL Model. According to concept of local composition, Renon and co-workers put forward the NRTL model.22 It is applied extensively in vapor−liquid and liquid−solid phase equilibrium. The expression of activity coefficient described by NRTL model for a component i is N

ln γi =

∑ j = 1 τjiGjixj N

∑i = 1 Gijx i

N

+

∑ j=1

N ⎡ ∑ xτG ⎤ ⎢τ − i = 1 i ij ij ⎥ ij N N ∑i = 1 Gijxj ⎢⎣ ∑i = 1 Gijx i ⎥⎦

xjGij

(9)

Gji = exp( −αjiτji)

(10)

αij = αji

(11)

τij = a ij + 385

bij T

(12) DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

a

386

4.09 −218.81 −4.978 1565.27 0.3 11.25

−26.685 11769 −4.586 2033.17 0.3 6.01

3.5032 22.118 −5.137 1756.86 0.3 7.42

a1 b1/K a2 b2/K α 104RMSD

RMSD = ((∑i N= 1(xci − xi)2)/N)1/2.

−4.175 1289.1 7845 −1.915 × 106 18.84

−4.905 1694.5 5463.4 −1.380 × 106 8.8

−4.394 1446.2 7057.1 −1.768 × 106 13.93

a1 b1/K a2 b2/K 104RMSD

0.3401 9834.82 34.33

0.1988 19501.9 16.3

0.2276 15606.7 24.51

−50.289 −1261.7 9.197 10.9

n-butanol

λ h 104RMSD

−151.9 2629.4 24.61 4.53

isopropyl alcohol

−103.98 806.93 17.32 7.12

n-propanol

A B C 104RMSD

parameter Modified Apelblat Equation −109.31 968.24 18.19 6.74 λh Equation 0.303 12321.7 20.18 Wilson Model −4.82 1578.8 7329 −1.844 × 106 8.84 NRTL Model 6.44 −1172.7 −5.774 1919.17 0.3 6.47

isobutyl alcohol

Table 4. Parameters of the Equations for 1,3,5-Trichlorobenzene in Different Solventa

2.076 −434.26 −3.914 1270.18 0.3 13.49

−6.745 1775.8 4977.5 −9.800 × 105 85.24

1.4745 2748.91 56.89

−46.892 −1186.5 8.709 9.86

cyclohexane

0.4754 −369.79 2.357 −109.64 0.3 20.59

−5.161 1152.4 3328.4 −3.876 × 105 66.81

1.5588 2053.93 35.16

31.055 −3798.8 −3.377 15.81

toluene

5.978 −977.07 −3.54 926.15 0.3 7.54

−2.743 644.81 4492.6 −8.121 × 105 11.95

0.4537 5403.5 42.62

−12.487 −2090.2 3.166 7.65

ethyl acetate

3.176 −172.15 −2.405 831.82 0.3 11.67

−2.218 648.52 4072.1 −8.585 × 105 10.97

0.1983 12390.7 27.28

−163.97 4197.1 25.93 12.28

acetone

Journal of Chemical & Engineering Data Article

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

aij and bij are interaction energy parameters and independent of temperature. The value of parameter α is from 0.2 to 0.47, which is in relation to the nonrandomness of the solution. In the present paper, α is taken as 0.3. The solubility of 1,3,5-trichlorobenzene at different temperatures is correlated with eqs 2−12 by means of a nonliner regression method. To evaluate the deference of the four models, the root-mean-square deviations (RMSD) and the relative average (RAD) deviation are employed. The RMSD is described as ⎡ ∑n (x c − x e)2 ⎤1/2 i i ⎥ RMSD = ⎢ i = 1 ⎢⎣ ⎥⎦ N

Based on the energetic point, the dissolution of a solid phase into a solvent relates the variation of thermodynamic properties, e.g., molar dissolution enthalpy (ΔsolHo). The change denotes the existence of the solid at its infinite dilution state at a given temperature. The activity coefficient of water at normal temperature is supposed to be 1, the change of molar dissolution enthalpy may be deduced from the Gibbs− Helmholtz equation:15 ⎛ d ln x ⎞ Δsol H o = R(T /K)2 ⎜ ⎟ ⎝ d(T /K) ⎠ p

Table 5 shows the obtained values of ΔsolHo of 1,3,5trichlorobenzene in different solvents. We can find from Table 5 that the molar dissolution enthalpy (ΔsolHo) for the dissolution procedure of 1,3,5-trichlorobenzene is positive. The positive values of ΔsolHo show that the dissolution of 1,3,5trichlorobenzene is an endothermic process in the selected solvents. It can also be found from Table 5 that the calculated molar dissolution enthalpies (ΔsolHo) for some systems seem to be relative high. To illustrate the case, a hypothetical scheme describing the dissolution process of a solid in a solvent is given in Figure 5, where T1 is the experimental temperature. The solution enthalpy approximately equals the summation of ΔHo1, ΔHo2, and ΔHo3. The value of ΔHo3 depends on the fusion temperature, experimental temperature, and the heat enthalpy of solute in the subcooled liquid state and in the solid state. Generally ΔH2o is greater than 0 because Tm (melting temperature) is greater than T1 (experimental temperature). In other words, the solution enthalpy minus enthalpy of fusion must not be equal to the excess enthalpy, but greater than the excess enthalpy. The difference between them depends on the values of ΔHo1 and ΔHo2. The so-called excess enthalpy is not the real excess enthalpy, but the macro one. So the relative high values of molar dissolution enthalpies (ΔsolHo) are reasonable. Figure 4 shows the dependence on temperature of the dissolution enthalpy of 1,3,5-trichlorobenzene in the studied solvents. It appears that there is a linear dependence between the dissolution enthalpy of 1,3,5-trichlorobenzene and temperature. As a result, we can conclude that the dissolution heat capacity does not vary throughout the dissolution process of 1,3,5-trichlorobenzene in these solvents. Figure 4 also illustrates that the dissolution enthalpy of 1,3,5-trichlorobenzene increases with an increase in temperature of the studied solvent except for toluene. The positive molar entropy of solution also shows that the entropy is the driving force for the dissolution process. The parameter λ in the λh equation is considered as the average association number of molecules of solute in solution. Table 4 further demonstrates that the λ values in all solvents are small; no obvious association arises throughout dissolution of the 1,3,5-trichlorobenzene in the studied solvents. The parameter h relates to the molar solution enthalpy of solute. The values of molar dissolution enthalpy are positive; there is repulsive interaction between the molecules of 1,3,5-trichlorobenzene and the solvent. Excess Enthalpy of the Solutions. By using the h value in eq 3 and enthalpy of fusion of 1,3,5-trichlorobenzene,26,27 the excess enthalpy of the dissolution HE, which can help us to acquire a more detailed understanding of solution characteristics, can be calculated by means of eq 17.20,29

(13)

And the relative average deviation (RAD) is defined as eq 14. RAD =

1 N

N

∑ i=1

(xie − xic) xie

(14)

The relative deviation (RD) between the experimental and calculated solubility is evaluated in terms of eq 15. RD =

xe − xc xe

(16)

(15)

Here N is the number of experimental points; xei denotes the experimental value, and xci is the calculated value. The melting temperature and enthalpy of fusion for 1,3,5trichlorobenzene were determined in the literature.26,27 In this work, the values determined by Linde and co-workers26 were used to correlate the solubility. The density 1,3,5-trichlorobenzene is taken from ref 28. The regressed values of A, B, and C in eq 2, λ and h in eq 3, ai and bi in eqs 6−8 and aij and bij in eqs 9−12), together with the root-mean-square deviations (RMSD) are shown in Table 4. In terms of the regressed values of parameters presented in Table 4, the calculated relative average deviation (RAD) and relative deviation (RD) are presented in Table 2. To illustrate the difference between the calculated solubility data and the experimental values, the calculated solubility data by the Apelblat equation are plotted in Figures 1 and 2. Tables 2 and 4 show that for the 1,3,5trichlorobenzene−isopropyl alcohol system, the value of RMSD (4.53 × 10−4) evaluated by Apelblat equation is smaller than those with the other three eqs (16.30 × 10−4, 8.80 × 10−4, 6.01 × 10−4 with λh equation, Wilson equation, and NRTL equation, respectively). For the systems of 1,3,5-trichlorobenzene−cyclohexane/toluene, RMSD values obtained with Wilson equation are larger than those with λh equation, while for other systems, the case is vice versa. The maximum RMSD value is 85.24 × 10−4, which is calculated by the Wilson equation for the 1,3,5-trichlorobenzene−cyclohexane system. The RAD values are all less than 2.02%. The phenomenon results from the different assumption for the two models. The solubility determined in the present work for 1,3,5-trichlorobenzene in pure solvents at studied temperature under 0.1 MPa provide good agreement with the values evaluated with the four models. We can draw the conclusion that the four models can all be used to correlate the solubility of 1,3,5trichlorobenzene in the selected solvents. Thermodynamic Properties for the Dissolution. Thermodynamic properties of dissolution are of great significance in providing a better method of studying the theoretical aspects of solution structure.

hR = ΔfusH + HE/x 387

(17) DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 5. Standard Dissolution Enthalpy of 1,3,5Trichlorobenzene in Eight Solvents at Different Temperaturesa ΔsolH0 T/K

a

kJ·mol

−1

273.15 275.65 278.15 280.65 283.15 285.65

32.63 32.99 33.35 33.71 34.07 34.43

273.15 275.65 278.15 280.65 283.15 285.65

34.03 34.54 35.05 35.56 36.07 36.59

273.15 275.65 278.15 280.65 283.15 285.65

31.38 31.57 31.76 31.95 32.14 32.33

273.15 275.65 278.15 280.65 283.15 285.65

33.27 33.65 34.02 34.4 34.78 35.16

280.65 283.15 285.65 288.15 290.65

30.18 30.37 30.55 30.73 30.91

273.15 275.65 278.15 280.65 283.15 285.65

23.91 23.84 23.77 23.70 23.63 23.56

273.15 275.65 278.15 280.65 283.15 285.65

24.57 24.63 24.7 24.77 24.83 24.9

273.15 275.65 278.15 280.65 283.15 285.65

23.99 24.53 25.07 25.61 26.15 26.69

ΔsolH0 T/K

−1

kJ·mol

n-Propanol 288.15 34.79 290.65 35.15 293.15 35.51 295.65 35.87 298.15 36.23 300.65 36.59 Isopropyl Alcohol 288.15 37.10 290.65 37.61 293.15 38.12 295.65 38.63 298.15 39.14 300.65 39.66 n-Butanol 288.15 32.52 290.65 32.71 293.15 32.91 295.65 33.1 298.15 33.29 300.65 33.48 Isobutyl Alcohol 288.15 35.54 290.65 35.91 293.15 36.29 295.65 36.67 298.15 37.05 300.65 37.43 Cyclohexane 293.15 31.09 295.65 31.27 298.15 31.45 300.65 31.63 303.15 31.81 Toluene 288.15 23.49 290.65 23.42 293.15 23.35 295.65 23.28 298.15 23.21 300.65 23.14 Ethyl Acetate 288.15 24.96 290.65 25.03 293.15 25.09 295.65 25.16 298.15 25.23 300.65 25.29 Acetone 288.15 27.23 290.65 27.77 293.15 28.31 295.65 28.84 298.15 29.38 300.65 29.92

ΔsolH0 T/K

kJ·mol−1

303.15 305.65 308.15 310.65 313.15

36.95 37.31 37.67 38.03 38.39

303.15 305.65 308.15 310.65 313.15

40.17 40.68 41.19 41.70 42.21

303.15 305.65 308.15 310.65 313.15

33.67 33.86 34.05 34.24 34.43

303.15 305.65 308.15 310.65 313.15

37.8 38.18 38.56 38.94 39.32

305.65 308.15 310.65 313.15

31.99 32.18 32.36 32.54

303.15 305.65 308.15 310.65 313.15

23.07 23.00 22.93 22.86 22.79

303.15 305.65 308.15 310.65 313.15

25.36 25.42 25.49 25.56 25.62

303.15 305.65 308.15 310.65 313.15

30.46 31.00 31.54 32.08 32.62

Figure 4. Enthalpy of dissolution of 1,3,5-trichlorobenzene in eight solvents at different temperatures: ■, n-propanol; ●, isopropyl alcohol; ▲, n-butanol; ▼, isobutyl alcohol; + , cyclohexane; ★, toluene; ×, ethyl acetate; ★, acetone.

Figure 5. Hypothetical dissolution process of a solid in a solvent.

where x denotes the solubility of 1,3,5-trichlorobenzene in solution in mole fraction and h is the parameter in the λh equation. The estimated values of the excess enthalpy of the solution are presented in Table 6 for each solution. The values of HE are positive in all solution systems studied except for toluene. The results may be explained according to the contribution of some kinds of interactions in solution.29 To overcome the cohesive forces of the solvent and decreased solubility, the cavity formation enthalpy (needed for solute accommodating) is endothermic. Besides, the (solute + solvent) interaction enthalpy is exothermic and depends mainly on interactions of hydrogen bonding and van der Waals forces. The positive values of dissolution enthalpy for 1,3,5-trichlorobenzene mixing with the studied solvents illustrate that the cross associating intermolecular interactions formed between 1,3,5-trichlorobenzene and the solvents are weaker than the self-associating interactions, which result in an endothermic solution process and the increasing values of HE with an increase in temperature. Similar behavior can also be found for other systems.29

■

CONCLUSION The solubility of 1,3,5-trichlorobenzene in eight pure organic solvents were determined experimentally at the temperatures ranging from (273.15/280.65 to 308.15) K. As temperature increased, the solubility data of 1,3,5-trichlorobenzene in pure solvents increased with various increments. At the same temperature, the solubility data of 1,3,5-trichlorobenzene in isopropyl alcohol are smaller than those in other solvens. They rank in the following order: toluene > cyclohexane > ethyl acetate > (n-butanol, acetone) > isobutyl alcohol > n-propanol > isopropyl alcohol. When the temperature is below 293.15 K, the solubility of 1,3,5-trichlorobenzene in acetone is larger than that in n-butanol, however the case is vice versa when the temperature is above 293.15 K. The modified Apelblat equation, λh equation, Wilson model, and NRTL model were used to correlate the experimental solubility data. The values of

Standard uncertainties u are u(T) = 0.02 K, u(ΔsolH0) = 0.1 kJ·mol−1. 388

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

Table 6. Excess Enthalpy of 1,3,5-Trichlorobenzene Solutions Studied at Several Temperatures and p = 101.3 kPa HE/kJ·mol−1 T/K

n-propanol

isopropyl alcohol

n-butanol

isobutyl alcohol

273.15 275.65 278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15

2.363 2.666 3.065 3.511 4.026 4.554 5.226 5.971 6.708 7.592 8.573 9.576 10.915 12.180 13.641 15.469 17.685

2.079 2.413 2.818 3.249 3.703 4.294 4.904 5.559 6.376 7.360 8.381 9.377 10.700 12.270 14.002 15.860 18.294

2.311 2.610 2.999 3.398 3.798 4.363 4.927 5.473 6.224 6.853 7.842 8.703 9.625 10.629 11.908 13.306 14.987

2.090 2.379 2.728 3.119 3.568 4.059 4.624 5.226 6.009 6.829 7.723 8.687 9.933 11.089 12.488 14.128 16.181

AUTHOR INFORMATION

Corresponding Author

*Tel: +86 576 85486698. Fax: +86 576 85137169. E-mail: lrr@ tzc.edu.cn. Funding

We thank the Natural Science Foundation of Zhejiang Province (Project number: LY14B030006) and Taizhou Science and Technology Plan Projects, China (Project number: 1402ky15) for their support. Furthermore, the National Natural Science Foundation of China (Project number: 21406192) and the Yangzhou City Science and Technology Bureau, China (Project number: 2012038-3 and YZ2011139) are also appreciated. Notes

The authors declare no competing financial interest.

■

toluene

ethyl acetate

acetone

0.587 0.658 0.74 0.832 0.929 1.033 1.143 1.282 1.426 1.57 1.75 1.946 2.155 2.369

−0.082 −0.089 −0.096 −0.106 −0.116 −0.126 −0.139 −0.150 −0.163 −0.178 −0.193 −0.207 −0.224 −0.242 −0.26 −0.278 −0.299

2.541 2.777 3.078 3.379 3.748 4.127 4.489 4.911 5.332 5.822 6.398 6.918 7.500 8.151 8.892 9.6300 10.394

3.580 4.034 4.479 4.965 5.499 6.138 6.755 7.486 8.229 9.072 9.901 11.008 11.989 13.135 14.648 16.396 18.206

(4) Mehilal, R. B.; Salunke; Agrawal, J. P. A Newly Developed Synthesis of 1,3,5-Trichlorobenzene (Sym. TCB) from Aniline. Indian J. Chem., Sect B 2002, 41 (B), 604−607. (5) Kazuyoshi, I.; Hiroaki, H. Preparation of 1,3,5-Trichlorobenzene with Zeolite Catalysts. JP Patent 0,4103,545, Apr 6, 1992. (6) Petruck, G. M.; Wambach, P. R. Process for the Preparation of 1,3,5-Trichlorobenzene. US Patent 4,409,407, Oct 11, 1983. (7) Kazuyoshi, I.; Hiroaki, H. Process for Isomerizing Trichlorobenzene. EP Patent 0,474,465, March 11, 1992. (8) Davis, M. C. Chlorination of Aniline and Methyl Carbanilate by N-Chlorosuccinimide and Synthesis of 1,3,5-Trichlorobenzene. Synth. Commun. 2009, 39, 1100−1108. (9) Gert, V.; Konrad, B.; Hans, W. Process for the Manufacture of 1,3,5-Trichlorobenzene. US Patent 4,306,103, Dec 15, 1981. (10) Ryuzo, N.; Kanichi, F.; Isao, Y.; Itaru, S.; Mikio, M. Process for Producing 1,3,5-Trichlorobenzene. US Patent 4,368,340, Jan 11, 1983. (11) Kazuyoshi, I.; Masatoshi, W. Production of 1,3,5-Trichlorobenzene. JP Patent 0,525,067, Feb 2, 1993. (12) Shiu, W. Y.; Wania, F.; Hung, H.; Mackay, D. Temperature Dependence of Aqueous Solubility of Selected Chlorobenzenes, Polychlorinated Biphenyls, and Dibenzofuran. J. Chem. Eng. Data 1997, 42, 293−297. (13) Yalkowsky, S. H.; Orr, R. J.; Valvani, S. C. Solubility and Partitioning. 3. The Solubility of Halobenzenes in Water. Ind. Eng. Chem. Fundam. 1979, 18, 351−353. (14) Zhao, H. K.; Ji, H. Z.; Meng, X. C.; Li, R. R. Solubility of 3Chlorophthalic Anhydride and 4-Chlorophthalic Anhydride in Organic Solvents and Solubility of 3-Chlorophthalic Acid and 4-Chlorophthalic Acid in Water from (283.15 to 333.15) K. J. Chem. Eng. Data 2009, 54, 1135−1137. (15) Zhao, H. K.; Xu, H.; Yang, Z. P.; Li, R. R. Solubility of 3,4Dichloronitrobenzene in Methanol, Ethanol, and Liquid Mixtures (Methanol + Water, Ethanol + Water): Experimental Measurement and Thermodynamic Modeling. J. Chem. Eng. Data 2013, 58, 3061− 3068. (16) Xu, H.; Zhang, B.; Yang, Z. P.; Yao, G. B.; Zhao, H. K. Solubility of Dichloronitrobenzene in Eight Organic Solvents from T = (278.15 to 303.15) K: Measurement and Thermodynamic Modeling. J. Chem. Eng. Data 2014, 59, 1281−1287. (17) Smallwood, I. M. Handbook of Organic Solvent Properties; Amold: London, 1996. (18) Apelblat, A.; Manzurola, E. Solubilities of L-glutamic Acid, 3Nitrobenzoic Acid, p-Toluic Acid, Calcium-L-lactate, Calcium Gluconate, Magnesium-DL-aspartate, and Magnesium-L-lactate in Water. J. Chem. Thermodyn. 2002, 34, 1127−1136.

relative average deviation are all smaller than 2.02%. The measured solubility for 1,3,5-trichlorobenzene in binary solutions at studied temperature under 0.1 MPa provide good agreement with the calculated values with the four models. The thermodynamic properties of solution, molar dissolution enthalpy (ΔsolH0) of 1,3,5-trichlorobenzene in pure solvents, were obtained. The values of ΔsolH0 are all positive and show that the dissolution process of 1,3,5-trichlorobenzene is endothermic in the selected solvents. The dissolution heat capacity remains constant during the dissolution process. Furthermore, the excess enthalpy of the solution is obtained for each solution.

■

cyclohexane

REFERENCES

(1) Hill, M.; Taylor, F., Jr. Notes-Nitration of 1,3,5-Trihalobenzenes. J. Org. Chem. 1960, 25, 1037−1038. (2) Nandi, A. K.; Kasar, S. M.; Thanigaivelan, U.; Mandal, A. K.; Pandey, R. K. Formation of the Sensitive Impurity 1,3,5-Triamino-2chloro-4,6-dinitrobenzene in Pilot Plant TATB Production. Org. Process Res. Dev. 2012, 16, 2036−2042. (3) Wolff, J. J.; Zietsch, A.; Oeser, T.; Bolocan, I. Rate Increase in Consecutive Nucleophilic Aromatic Substitution Reactions of Trichlorotrinitrobenzene: The Synthesis of 1-(Alkylamino)-3,5dichloro-2,4,6-trinitrobenzenes. J. Org. Chem. 1998, 63, 5164−5168. 389

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390

Journal of Chemical & Engineering Data

Article

(19) Apelblat, A.; Manzurola, E. Solubilities of o-Acetylsalicylic, 4Aminosalicylic, 3,5-Dinitrosalicylic, And p-toluic Acid, and Magnesium-DL-aspartate in Water from T = (278 to 348) K. J. Chem. Thermodyn. 1999, 31, 85−91. (20) Buchowski, H.; Ksiazczak, A.; Pietrzyk, S. Solvent Activity along a Saturation Line and Solubility of Hydrogen-Bonding Solids. J. Phys. Chem. 1980, 84, 975−979. (21) Wilson, G. M. Vapor-Liquid Equilibrium. XI. A New Expression for the Excess Free Energy of Mixing. J. Am. Chem. Soc. 1964, 86, 127−130. (22) Renon, H.; Prausnitz, J. M. Estimation of Parameters for the NRTL Equation for Excess Gibbs Energies of Strongly Nonideal Liquid Mixtures. Ind. Eng. Chem. Process Des. Dev. 1969, 8, 413−419. (23) Wang, K.; Hu, Y. H.; Yang, W.; Guo, S.; Shi, Y. Measurement and Ccorrelation of the Solubility of 2,3,4,5-Tetrabromothiophene in Different Solvents. J. Chem. Thermodyn. 2012, 55, 50−55. (24) Smith, J. M.; Ness, H. C. V.; Abbott, M. M. Introduction to Chemical Engineering Thermodynamics; McGraw-Hill: New York, 2001. (25) Stanley, M. W. Phase Equilibria in Chemical Engineering; Butterworth: New York, 1985. (26) van der Linde, P. R.; van Miltenburg, J. C.; van den Berg, G. J. K.; Oonk, H. A. J. Low-Temperature Heat Capacities and Derived Thermodynamic Functions of 1,4-Dichlorobenzene, 1,4-Dibromobenzene, 1,3,5-Trichlorobenzene, and 1,3,5-Tribromobenzene. J. Chem. Eng. Data 2005, 50, 164−172. (27) Acree, W. E., Jr. Thermodynamic Properties of Organic Compounds: Enthalpy of Fusion and Melting Point Temperature Compilation. Thermochim. Acta 1991, 189, 37−56. (28) Han, S.; Yao, G. B.; Zhong, Y. H.; Du, C. B.; Meng, L.; Zhao, H. K. Measurement and Modeling for Isobaric Vapor−Liquid Equilibrium of Binary 1,3,5-Trichlorobenzene + 3,5-Dichloroaniline and 3Chloroaniline + 3,5-Dichloroaniline Systems. Ind. Eng. Chem. Res. 2015, 54, 3706−3710. (29) Fang, J.; Zhang, M. J.; Zhu, P. P.; Ouyang, J. B.; Gong, J. B.; Chen, W.; Xu, F. X. Solubility and Solution Thermodynamics of Sorbic Acid in Eight Pure Organic Solvents. J. Chem. Thermodyn. 2015, 85, 202−209.

390

DOI: 10.1021/acs.jced.5b00607 J. Chem. Eng. Data 2016, 61, 380−390