Article pubs.acs.org/jced
Solubility of 1,3,5-Benzenetricarboxylic Acid in Different Solvents Dan Zhang*,†,‡ and Qian Xu§ †
School of Materials Science and Metallurgy, Northeastern University, Shenyang 110004, P. R. China School of Chemistry and Materials Science, Liaoning Shihua University, Fushun 113001, P. R. China § State Key Laboratory of Advanced Special Steel, Shanghai University, Shanghai 200072, P. R. China ‡
ABSTRACT: The solubility of 1,3,5-benzenetricarboxylic acid in pure water, isopropyl alcohol, isobutyl alcohol, methanol, ethanol, and ethylene glycol were measured at the temperature range from 298 to 360 K. The order of solubility of 1,3,5benzenetricarboxylic acid was ethanol > methanol > ethylene glycol > isobutanol > isopropyl alcohol > water. In addition, the Apelblat equation was used to correlate the solubility with temperature in different solvents.
■
acid by cooling crystallization.3 The improvement and optimization of the crystallization process is important to obtain products with higher purity; therefore the precise and adequate solubility data are indispensable. Thus, solubility is always regarded as the critical data needed for the crystallization process development including the solvent selection, process optimization, etc. Unfortunately, no experimental solubility data of 1,3,5-benzenetricarboxylic acid in organic solvents was reported, except for that in acetic acid−water.4 In this article, the solubilities of 1,3,5-benzenetricarboxylic acid in different solvents were measured at temperatures from 298 to 360 K and correlated by the modified Apelblat model.
INTRODUCTION 1,3,5-Benzenetricarboxylic acid is an important chemical intermediates, which is the primary downstream product of 1,3,5-trimethylbenzene. The melting point of 1,3,5-benzenetricarboxylic acid is 380 °C, and the molecular structure is given in Figure 1. 1,3,5-Benzenetricarboxylic acid is widely used in
■
EXPERIMENTAL SECTION Materials. 1,3,5-Benzenetricarboxylic acid with mass fraction purity higher than 99.5% was purchased from J&K Scientific Ltd. Methanol, isopropyl alcohol, isobutyl alcohol, ethanol, and ethylene glycol were analytical grade reagents from Tianjin Guangfu Chemical Reagent Co., and distilled deionized water of HPLC grade was used. Detailed information on the materials was shown in Table 1. Apparatus and Procedure. The solubilities of 1,3,5benzenetricarboxylic acid in different solvents were measured by a synthetic method with a laser monitoring observation technique. The procedure and apparatus of the solubility measurement is the same as those in the literature.5,6 The laser monitoring system was made up of a laser generator, a photoelectric transformer, and a light intensity display. The laser beam penetrated the solution to detect the solid in it. The solution was placed in a jacketed glass vessel, in which the temperature was controlled through a water bath. The temperature was monitored by a mercury-in-glass thermometer
Figure 1. Chemical structure of 1,3,5-benzenetricarboxylic acid.
plastics, synthetic fiber, resin, plasticizer, fungicides, antiseptic, cross-linking agent, and reverse osmosis membrane materials.1 Especially, it has been extensively used as a kind of important organic ligands in the application of synthesis for metal organic frameworks (MOFs).2 The major production methods of 1,3,5-benzenetricarboxylic acid are the potassium permanganate oxidation, the nitric acid oxidation, and the liquid phase oxidation by air. The first two methods have some obvious disadvantages, such as low reaction efficiency, large amount of wastewater and residue, strong corrosion, and high risk of operation. Usually, the liquid phase oxidation by air is the main industrial production process of 1,3,5-benzenetricarboxylic acid, with the advantage of lower production costs and higher selectivity and yield. The raw product of 1,3,5-benzenetricarboxylic acid from the liquid phase oxidation by air needs to be purified by crystallization in an acetic acid−water binary solvent. However, the acetic acid−water solvent has an adverse impact on the corrosion of equipment. To overcome the shortcoming, ethanol was selected as the solvent to refine 1,3,5-benzenetricarboxylic © XXXX American Chemical Society
Received: October 14, 2015 Accepted: January 8, 2016
A
DOI: 10.1021/acs.jced.5b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 1. Description of Materials Used in This Article chemical name
source
initial mass fraction purity
purification method
final mass fraction puritya
analysis method
1,3,5-benzenetricarboxylic acid methanol isopropyl alcohol isobutyl alcohol ethanol ethylene glycol
J&K Scientific Ltd. Tianjin Guangfu Chemical Reagent Co. Tianjin Guangfu Chemical Reagent Co. Tianjin Guangfu Chemical Reagent Co. Tianjin Guangfu Chemical Reagent Co. Tianjin Guangfu Chemical Reagent Co.
0.995 0.995 0.995 0.995 0.995 0.995
none none none none none none
NA NA NA NA NA NA
none none none none none none
a
NA = not applicable.
■
RESULTS AND DISCUSSION Solubility of 1,3,5-Benzenetricarboxylic Acid in Different Solvents. The solubility of 1,3,5-benzenetricarboxylic acid in water, isopropyl alcohol, isobutyl alcohol, methanol, ethanol, and ethylene glycol at temperatures ranging from 298 to 360 K were presented in Figure 2, and the comparison of the solubility of 1,3,5-benzenetricarboxylic acid in water between the literature7 and this work has been given in Figure 3.
Figure 2. Solubility (x3) of 1,3,5-benzenetricarboxylic acid in pure solvents: □, water; △, isopropyl alcohol; ○, isobutyl alcohol; ▽, methanol; ☆, ethanol; ◇, ethylene glycol.
with the uncertainty of ±0.01 K. During the experiment, a certain amount of solvents were introduced to the vessel, and 1,3,5-benzenetricarboxylic acid was added after weighing. The solution was stirred continuously at the required temperature, and the dissolution of 1,3,5-benzenetricarboxylic acid was examined by the laser beam penetrating the vessel. 1,3,5-Benzenetricarboxylic acid was added slowly until it could not be dissolved completely, and the intensity of the laser beam penetrating the vessel reached the minimum, indicating that the solution was saturated. The total addition of 1,3,5-benzenetricarboxylic acid was recorded. Thus, the molar fraction of the solubility x3 could be calculated by eq 1. At each composition and temperature, the measurement was repeated three times and the average values were used to calculate the solubility. And the composition of solvent mixtures w1 was defined as eq 2. x3 =
m3 /M3 m1/M1 + m2 /M 2 + m3 /M3
(1)
w1 =
m1 m1 + m2
(2)
Figure 3. Comparison of the solubility of 1,3,5-benzenetricarboxylic acid in water between the literature7 (○) and this work (△).
where m1 represents the mass of water, m2 represents the mass of organic solvents, m3 represents the mass of 1,3,5benzenetricarboxylic acid. M1, M2, and M3 are the molecular weight of water, organic solvents, and 1,3,5-benzenetricarboxylic acid, respectively. The relative standard uncertainty was less than 2% which was calculated from the standard deviations of repeated experimental measurements.
Figure 4. Solubility (x3) of 1,3,5-benzenetricarboxylic acid in ethanol− water binary solvents: □, 90 wt % H2O; △, 80 wt % H2O; ○, 70 wt % H2O; ▽, 60 wt % H2O; ☆, 50 wt % H2O; ◇, 40 wt % H2O; ⊙, 20 wt % H2O. B
DOI: 10.1021/acs.jced.5b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 2. Solubility of 1,3,5-Benzenetricarboxylic Acid in Pure Solvents at 101.325 kPa from 298 to 360 Ka T/K
103x3
103x3cal
301.05 305.47 309.80 315.22 320.56 325.11 329.42
0.15 0.19 0.25 0.33 0.44 0.55 0.69
0.15 0.19 0.24 0.33 0.43 0.55 0.69
305.77 311.02 315.67 320.61 324.58 330.39
7.06 7.98 8.69 9.49 10.42 11.67
7.16 7.90 8.64 9.55 10.36 11.72
306.00 310.65 314.94 319.87 324.75 330.58
7.80 8.60 9.26 10.45 11.67 13.24
7.73 8.57 9.41 10.48 11.65 13.20
298.21 304.67 308.78 313.97
12.03 13.84 15.12 16.85
12.04 13.85 15.10 16.82
302.89 309.85 312.83 319.06 324.50
20.70 22.83 23.68 25.70 27.67
20.71 22.77 23.71 25.79 27.73
305.44 310.56 315.85 321.33 326.03 331.84
8.26 9.51 11.24 13.05 14.75 17.78
8.10 9.47 11.10 13.06 14.97 17.68
AAD
T/K
water 1.65 333.45 0.59 337.32 1.59 342.37 1.68 346.86 1.91 350.93 0.06 354.70 1.04 isopropyl alcohol 1.32 336.05 1.02 339.51 0.52 342.69 0.57 348.82 0.59 353.47 0.36 isobutyl alcohol 0.92 336.27 0.42 340.92 1.65 345.49 0.33 350.32 0.17 354.87 0.32 methanol 0.09 319.01 0.05 323.32 0.09 328.20 0.19 ethanol 0.06 328.86 0.27 334.40 0.14 338.61 0.35 343.30 0.22 348.03 ethylene glycol 1.96 336.56 0.38 341.48 1.26 345.80 0.04 350.33 1.53 355.22 0.56 359.89
103x3
103x3cal
Table 3. Solubility of 1,3,5-Benzenetricarboxylic Acid in Ethanol−Water Binary Solvents at 101.325 kPa from 302 to 345 Ka
AAD
T/K 0.85 1.03 1.33 1.65 2.05 2.48
0.85 1.03 1.33 1.67 2.04 2.46
0.16 0.55 0.44 1.44 0.12 0.6
13.22 14.21 15.49 17.68 20.04
13.25 14.31 15.37 17.68 19.71
0.24 0.70 0.77 0.04 1.68
14.96 16.41 18.07 19.96 21.62
14.90 16.44 18.10 20.01 21.99
0.40 0.16 0.12 0.26 1.69
18.65 20.20 22.36
18.63 20.29 22.32
0.11 0.46 0.19
29.60 31.55 33.29 35.46 37.87
29.39 31.62 33.42 35.53 37.78
0.73 0.22 0.39 0.19 0.23
20.21 22.89 26.16 29.32 33.60 38.07
20.20 23.15 26.06 29.46 33.57 37.96
0.08 1.14 0.38 0.48 0.11 0.31
a
x3 is the experimental solubility of 1,3,5-benzenetricarboxylic acid in pure solvents. x3cal is the calculated solubility of 1,3,5-benzenetricarboxylic acid in pure solvents. AAD is the average absolute deviation. Standard uncertainties u for temperature T and pressure P are u(T) = 0.01 K and u(P) = 5 kPa. The relative standard uncertainty ur for the solubility x3 is ur (x3) = 0.25.
103x3
103x3cal
302.03 306.75 311.61 316.10 320.67
0.29 0.41 0.58 0.82 1.15
0.29 0.41 0.59 0.82 1.14
302.26 306.93 311.87 316.70 321.57
1.48 1.88 2.30 2.84 3.51
1.48 1.86 2.33 2.87 3.50
302.31 306.86 311.78 316.47 321.46
4.95 5.62 6.60 7.57 8.78
4.93 5.70 6.63 7.61 8.75
302.35 306.84 311.72 316.61 321.46
5.60 6.41 7.36 8.45 9.37
5.65 6.42 7.35 8.38 9.49
302.10 306.93 311.82 316.72 321.62
13.25 14.67 16.41 18.07 20.03
13.32 14.81 16.39 18.05 19.78
302.07 306.87 311.77 316.62 321.50
16.50 18.11 19.88 21.86 23.67
16.48 18.12 19.89 21.71 23.61
302.24 306.85 311.77 316.63 321.53
19.12 20.43 22.02 23.93 25.51
19.01 20.48 22.14 23.86 25.69
T/K
AAD
w1 = 0.9 1.64 325.26 1.19 329.50 1.78 336.22 0.79 340.56 0.54 345.35 w1 = 0.8 0.23 326.35 1.16 331.26 1.33 336.16 1.05 341.04 0.17 345.78 w1 = 0.7 0.43 326.05 1.54 331.21 0.45 335.77 0.55 340.47 0.42 345.21 w1 = 0.6 0.95 326.23 0.21 330.78 0.14 335.62 0.90 339.85 1.28 344.82 w1 = 0.5 0.54 326.37 0.89 331.08 0.11 335.91 0.13 340.58 1.23 345.30 w1 = 0.4 0.13 326.27 0.08 330.97 0.05 335.88 0.68 340.52 0.26 345.23 w1 = 0.2 0.56 326.32 0.28 331.21 0.51 336.13 0.28 340.96 0.68 345.70
103x3
103x3cal
AAD
1.59 2.08 3.36 4.47 6.10
1.58 2.12 3.34 4.46 6.10
0.71 1.82 0.70 0.21 0.13
4.29 5.03 5.98 7.03 8.14
4.22 5.05 6.00 7.05 8.18
1.60 0.40 0.25 0.36 0.59
9.98 11.40 12.54 14.05 15.65
9.89 11.28 12.61 14.08 15.66
0.88 1.03 0.59 0.22 0.08
10.75 12.05 13.31 14.72 16.34
10.69 11.93 13.35 14.69 16.38
0.58 1.07 0.29 0.22 0.27
21.82 23.01 25.26 26.71 29.25
21.53 23.32 25.21 27.08 29.01
1.33 1.34 0.22 1.38 0.82
25.32 27.36 29.79 31.59 33.83
25.54 27.51 29.61 31.66 33.77
0.88 0.54 0.59 0.20 0.18
27.79 29.48 31.65 34.03 35.99
27.56 29.57 31.69 33.86 36.09
0.82 0.32 0.10 0.48 0.29
a
w1 is the mass fraction of water in ethanol−water binary solvents. x3 is the experimental solubility of 1,3,5-benzenetricarboxylic acid in ethanol−water binary solvents. x3cal is the calculated solubility of 1,3,5-benzenetricarboxylic acid in ethanol−water binary solvents. AAD is the average absolute deviation. Standard uncertainties u for temperature T and pressure P are u(T) = 0.01 K and u(P) = 5 kPa. The relative standard uncertainty ur for the mass fraction of water w2 and the solubility x3 is ur (w1) = 0.1% and ur (x3) = 0.25.
From Figure 2, it can be found that the solubility of 1,3,5benzenetricarboxylic acid increases with the rising of temperature in the six pure solvents. The order of solubility of 1,3,5-benzenetricarboxylic acid is ethanol > methanol > ethylene glycol > isobutyl alcohol > isopropyl alcohol > water. From Figure 3, it can be seen that the tendency of solubility for the literature7 and this work is consistent under the same temperature range, indicating that the solubility measurement was reliable. Furthermore, the solubility of 1,3,5-benzenetricarboxylic acid in ethanol−water binary solvents at temperatures ranging from 302 to 346 K were measured and presented in Figure 4. From Figure 4, it can be found that the solubility of 1,3,5-benzenetricarboxylic acid increases with the increase of
Table 4. Regression Parameters and rmsd of Apelblat Equation of 1,3,5-Benzenetricarboxylic Acid in Pure Solvents
C
solvents
A
B
C
R2
rmsd
water isopropyl alcohol isobutyl alcohol methanol ethanol ethylene glycol
−136.91 −163.89 −62.93 −19.53 −39.07 −51.08
1823.23 6082.81 1191.28 −679.44 831.08 −34.80
22.60 25.51 10.67 4.26 6.89 9.31
0.99985 0.99815 0.99964 0.99985 0.99967 0.99982
0.01 0.12 0.13 0.04 0.10 0.14
DOI: 10.1021/acs.jced.5b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 5. Regression Parameters and rmsd of Apelblat Equation of 1,3,5-Benzenetricarboxylic Acid in Ethanol−Water Binary Solvents solvent
A
B
C
R2
100rmsd
w1 = 0.9 w1 = 0.8 w1 = 0.7 w1 = 0.6 w1 = 0.5 w1 = 0.4 w1 = 0.2
−101.05978 144.82654 71.16119 25.30473 63.18624 48.14494 −6.83395
−1426.27588 −10334.46689 −5681.68535 −3323.93851 −4467.82515 −3619.46010 −832.62994
18.30739 −19.30222 −8.88650 −2.20242 −8.02127 −5.84186 2.19458
0.99993 0.99957 0.99967 0.99959 0.99819 0.99956 0.99956
0.02 0.03 0.06 0.07 0.21 0.12 0.13
■
temperature, while it decreases with increasing water content in the solvent mixtures. The solubility of 1,3,5-benzenetricarboxylic acid was the highest in pure ethanol. The results of the solubility in pure solvents provided guidance for the cooling crystallization of 1,3,5-benzenetricarboxylic acid with ethanol as solvent, while the results of the solubility in ethanol−water binary solvents can be used to optimize the process of antisolvent crystallization of 1,3,5-benzenetricarboxylic acid. Correlation of Solubility of 1,3,5-Benzenetricarboxylic Acid. The relationship between the solubility and temperature can be correlated by the modified Apelblat model as follows:8,9 ln x3 = A +
B + C ln T T
*Tel.: +86-24-83684943. Fax: +86-24-83687731. E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
■
xi − xical × 100 xi
(3)
(4)
The root-mean-square deviations (rmsd) is calculated by eq 5 for assessing the accuracy of the modified Apelblat model. ⎡1 rmsd = ⎢ ⎢⎣ n
⎤1/2 cal 2 ⎥ ( x x ) − ∑ i i ⎥⎦ i=0
REFERENCES
(1) Sikkenga, D. L.; Pandya, A. K.; Zaenger, I. C.; Abrams, K. J.; Bartos, T. M. Production of high purity aromatic carboxylic acid by oxidation in benzoic acid and water solvent. U.S. Patent 6562997, 2003. (2) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n. Science 1999, 283, 1148−1150. (3) Xu, Y.; Chen, S. H.; Xing, Y. J.; Zhou, Y. B.; Wang, K. X.; Du, W. B.; Xu, Y. X.; Wang, Y. C. A purifying method for crude 1,3,5benzenetricarboxylic acid. CN. Patent 104513156, 2013. (4) Feng, L.; Wang, Q. B.; Li, X. Solubilities of 1,3,5-benzenetricarboxylic acid and 1,3-benzenedicarboxylic acid in acetic acid + water solvent mixtures. J. Chem. Eng. Data 2008, 53, 2501−2504. (5) Guo, H.; Song, L. C.; Yang, C. H.; Tao, Y.; Long, Y. J.; Cui, Y. B. Solubility of clopidogrel hydrogen sulfate (Form II) in ethanol plus cyclohexane mixtures at (283.35 to 333.75) K. J. Chem. Eng. Data 2015, 60, 545−550. (6) Ren, G. B.; Wang, J. K.; Yin, Q. X.; Zhang, M. J. Solubilities of proxetine hydrochloride hemihydrate between 286 and 363 K. J. Chem. Eng. Data 2004, 49, 1671−1674. (7) Apelblat, A.; Manzurola, E.; Balal, N. A. The solubilities of benzene polycarboxylic acids in water. J. Chem. Thermodyn. 2006, 38, 565−571. (8) Liu, Z. K.; Yin, Q. X.; Zhang, X. W.; Zhang, H.; Gong, J. B.; Wang, J. K. Measurement and correlation of the solubility of 4,4′- oxydianiline different organic solvents. Fluid Phase Equilib. 2013, 356, 38−45. (9) Zhang, X. W.; Yin, Q. X.; Gong, J. B.; Liu, Z. K. Solubility of 5amino-N,Nbis(2,3- dihydroxypropyl)-2,4,6-triiodobenzene-1,3-dicarboxamide in ethanol + water mixtures. J. Chem. Eng. Data 2010, 55, 2355−2357.
where x3 is the mole fraction solubility of 1,3,5-benzenetricarboxylic acid, T is the absolute temperature, and A, B, C are the empirical parameters. The average absolute deviation (AAD) is defined as follows: AAD =
AUTHOR INFORMATION
Corresponding Author
n
(5)
where n is the number of experimental points and xi and xcal i represent the experimental and calculated values of the solubility, respectively. The experimental solubility of 1,3,5-benzenetricarboxylic acid in pure solvents and ethanol−water binary solvents at different temperatures was correlated by the modified Apelblat model. The calculated values of solubility were listed in Table 2 and Table 3, and the values of the parameters (A, B, C) for the modified Apelblat model were listed in Table 4 and Table 5. It can be seen that the solubility data in different solvents could be described by the modified Apelblat model with higher accuracy at the temperature range from 298 to 360 K.
■
CONCLUSIONS The solubility of 1,3,5-benzenetricarboxylic acid in different solvents were determined at temperatures from 298 to 360 K. The experimental data were correlated by the modified Apelblat model. The experimental results showed that the solubility of 1,3,5-benzenetricarboxylic acid in different solvents increases with an increase in temperature. The correlation results illustrated that the modified Apelblat model was a proper model to describe the relationship between the solubility data of 1,3,5-benzenetricarboxylic acid and temperature. D
DOI: 10.1021/acs.jced.5b00870 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
