Article pubs.acs.org/jced
Solubilities of Adipic Acid in Cyclohexanol + Cyclohexanone Mixtures and Cyclohexanone + Cyclohexane Mixtures Ximeng Yu, Zhongquan Shen, Qing Sun, Nianlong Qian, Chao Zhou, and Jizhong Chen* College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China S Supporting Information *
ABSTRACT: The solubilities of adipic acid in cyclohexanol + cyclohexanone mixtures from 303.0 to 353.0 K and in cyclohexanone + cyclohexane mixtures from 303.0 to 378.5 K were determined using a titration and an in situ ATR-FTIR method. The averaged relative deviation between two methods at given temperatures was less than 2%. The solubility of adipic acid in cyclohexanone + cyclohexane mixtures increases with increasing mass fraction of cyclohexanone in the mixtures at given temperatures. However, the solubility of adipic acid in cyclohexanol + cyclohexanone mixtures reaches the maximum at cyclohexanone mass fraction of 0.4. The experimental data were well correlated by Apelblat equation and λh equation. The thermodynamics functions of the dissolution process were calculated by van’t Hoff equation.
1. INTRODUCTION Adipic acid (1,6-hexanedioic acid, Scheme 1) is a feedstock for producing nylon-6,6 and has a worldwide market of more than 2.5 million tons annually.1,2
cyclohexane system and the adipic acid + cyclohexanol + cyclohexanone system under higher temperatures. To supplement fundamental data for the production of adipic acid, the solubilities of adipic acid in cyclohexanol + cyclohexanone mixtures from 303.0 to 353.0 K and in cyclohexanol + cyclohexanone mixtures from 303.0 to 358.0 K was determined using a titration analysis in this work. Furthermore, an in situ ATR-FTIR (attenuated total reflectionFourier transform infrared) method was applied to measure the solubility of adipic acid in pure cyclohexanol, cyclohexanone, and cyclohexanone + cyclohexane mixtures under higher temperatures. The experimental solubility data were also correlated by the Apelblat equation and λh equation. The thermodynamics functions of the dissolution process of adipic acid in the solvent mixtures were calculated by van’t Hoff equation.
Scheme 1. Chemical Structure of Adipic Acid
Solubility data of adipic acid is important not only for separation and purification but also for synthesis processes.3,4 Recently, solubilities of adipic acid in several solvents such as cyclohexanol,5,6 cyclohexanone,5,6 acetone,3,7 chloroform,7,8 acetic acid + water mixtures, and acetic acid + cyclohexane mixtures or in the presence of other dibasic acid such as glutaric acid + acetone or n-butanol mixtures were measured by different methods including titration,9 HPLC,6 laser detecting system, ATR-FTIR spectroscopy, and so forth.4,10−13 However, most of solubility curves of adipic acid were obtained under temperatures lower than 355.0 K for crystallization process,4,5,7−9 which likely results from the difficulty sampling solutions at higher temperatures.6,14 Furthermore, few available solubility data was reported for new synthesis routes of adipic acid, such as oxidation of cyclohexanone in cyclohexane using microreactor technology and oxidation of KA oil (the mixtures of cyclohexanol and cyclohexanone) with air or O2 as oxidant instead of traditional HNO3,15−20 which emits huge amount of N2O.21 In this sense, it is essential to obtain solid−liquid equilibria data of the adipic acid + cyclohexanone + © XXXX American Chemical Society
2. EXPERIMENTAL SECTION 2.1. Materials. Adipic acid (AR grade), cyclohexanone (AR grade), cyclohexane (AR grade), and cyclohexanol (CA grade) were purchased from Sinopharm Chemical Reagent Co., Ltd. Adipic acid was dried at 120 °C for 2 h and kept in a desiccator with dry silica gel. Its melting point temperature Tm was determined by differential scanning calorimetry (PE, DSC 7) and the value is 425.5 ± 0.5 K, which agrees with the published data.7,8 Cyclohexanol was refluxed with freshly ignited CaO for 2 h and then fractionally distilled to collect fraction with purity higher than 99.0% analyzed by gas chromatography (Shimadzu Received: October 16, 2015 Accepted: January 19, 2016
A
DOI: 10.1021/acs.jced.5b00880 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 1. Source and Purities of the Materials
a b
material
molecular formula
mass fraction
purification method
analysis method
final mass fraction
source
adipic acida cyclohexanol cyclohexanone cyclohexane sodium hydroxide
C6H10O4 C6H12O C6H10O C6H12 NaOH
≥99.5% ≥98.0% ≥99.5% ≥99.5% ≥96.0%
drying distillation none none none
titration GCb GC GC titration
≥99.5% ≥99.0% ≥99.5% ≥99.5% ≥96.0%
Sinopharm Sinopharm Sinopharm Sinopharm Sinopharm
Melting point temperature Tm is 425.5 ± 0.5 K, determined at pressure p = 0.1 MPa, and standard uncertainties are u(Tm) = 0.5 K and ur(p) = 0.05. GC, gas chromatography.
GC-2014).22 Cyclohexanone and cyclohexane were used directly. Distilled water was used in the experiments. A detailed description of the materials used in the work is listed in Table 1. 2.2. Apparatus and Procedures. 2.2.1. Analytical Method. The solubility of adipic acid in the solvents under lower temperatures in this work was determined by an analytical method, which is widely used for solubility determination in literatures.7−9 A 100 mL flask with a reflux condenser, a magnetic stirring rotor and a thermocouple was used as the experimental apparatus and mounted in a silicon oil bath. The solution temperature was monitored by a thermocouple with an uncertainty of 0.1 K. In each experiment, an excess amount of adipic acid was added into 50.00 ± 0.02 g binary solvents in the flask, the mixture was stirred at least for 4 h, and then was kept in a static state isothermally for more than 2 h. The upper saturated solution (1 g, accurate to 0.1 mg) was sampled using a preheated glass pipet and analyzed by an acid− base titration. The solid−liquid equilibrium was achieved until repetitive measurements being reproducible within ±3% during the following several hours. It was found that 2 h after stopping stirring was enough for undissolved adipic acid solids to precipitate completely. For assurance, the mixture was left undisturbed at least for 4 h to ensure thorough settlement. The upper solution was taken for titration using NaOH standard solution of 0.1 mol·L−1 and 0.05 mol·L−1 for cyclohexanol + cyclohexanone system and for cyclohexanone + cyclohexane system, respectively. Each analysis was repeated three times with a mean relative deviation of 1.0%. The solubilities of adipic acid in cyclohexanol + cyclohexanone mixtures and in cyclohexanone + cyclohexane mixtures were measured from 303.0 to 353.0 K and from 303.0 to 358.0 K, respectively. 2.2.2. In Situ ATR-FTIR Method. Considering sampling errors of analytical method at higher temperatures, some efforts have been taken to overcome the problem.6,14 In situ ATRFTIR technology has been successfully used for real-time monitoring and tracking of the crystallization and reaction process23−25 and for solubility determination without any sampling operation.3,26 In this work an in situ ATR-FTIR was applied to determine the solubility of adipic acid in given solvents under higher temperatures. The in situ ATR-FTIR measurements were performed in the apparatus above-mentioned using a MettlerToledo ReactIR iC10 spectrometer. The base unit contains a mercuric cadmium telluride (MCT) detector, a silver halide fiber conduit (9.5 mm × 1.5 m) and a probe which was inserted into the solution (seeing Figure 1). The experimental solutions were prepared by successive addition of adipic acid (accurate to 0.1 mg) into the solvents of 50.00 ± 0.02 g. The real-time IR spectra of adipic acid in the solution were collected at 15 s intervals with each spectrum averaged over 32 scans by the FTIR probe from 2800 to 650
Figure 1. Experimental apparatus: 1, condenser; 2, thermocouple; 3, silicone oil bath; 4, magnetic stirring rotor; 5, temperature and stirrer controller; 6, elevator; 7, flask; 8, ATR-FTIR fiber conduit and probe.
cm−1at 8 wavenumber resolution. The solubility of adipic acid in given solvents was determined through a calibration curve obtained.3 The solubilities of adipic acid in pure cyclohexanol and pure cyclohexanone from 303.0 to 388.8 K and in cyclohexanone + cyclohexane mixtures from 363.0 to 378.5 K were obtained using the in situ FTIR method, respectively. 2.3. Verification of the Experimental Methods. To verify the reliability of titration analysis in this work, the solubility of adipic acid in water was measured (experimental data seeing Table S1 in Supporting Information) and compared with the published data.5−7,28 As shown in Figure 2, the mole fraction solubility (x1) experimentally obtained herein is in good accordance with the other published data except for data above 330.0 K reported by Suren.6 Furthermore, another five
Figure 2. Solubility of adipic acid in water: ■, experimental values; purple ▽, literature values;5 blue △, literature values;6 red ○, literature values;7 green ◇, literature values.28 B
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Table 2. Solubilities of Adipic Acid (1) in Cyclohexanol (2) + Cyclohexanone (3) Mixture at Temperature T and Pressure p = 0.1 MPaa T/K 303.0 313.0 323.0 333.0 343.0 353.0 303.0 313.0 323.0 333.0 343.0 353.0
102 x1
b 102 xeq1 1
w3 = 0.0 2.276 2.236 3.601 3.745 5.862 5.819 8.728 8.455 11.372 11.567 14.988 14.996 w3 = 0.2 4.003 4.019 6.023 5.978 8.425 8.423 11.242 11.310 14.548 14.541 18.012 17.983
RD/%c
T/K
1.76 4.01 0.73 3.13 1.72 0.05
303.0 313.0 323.0 333.0 343.0 353.0
0.39 0.75 0.02 0.60 0.05 0.16
303.0 313.0 323.0 333.0 343.0 353.0
b 102 xeq1 1
102 x1
w3 = 0.4 4.254 4.238 6.521 6.607 9.700 9.532 12.688 12.833 16.311 16.242 19.436 19.454 w3 = 0.6 3.499 3.496 5.356 5.374 7.802 7.760 10.537 10.594 13.804 13.755 17.054 17.073
RD/%c
T/K
0.38 1.33 1.73 1.14 0.42 0.09
303.0 313.0 323.0 333.0 343.0 353.0
0.10 0.35 0.54 0.54 0.36 0.11
303.0 313.0 323.0 333.0 343.0 353.0
102 x1
b 102 xeq1 1
w3 = 0.8 2.861 2.861 4.433 4.398 6.304 6.412 8.924 8.918 12.101 11.890 15.117 15.258 w3 = 1.0 1.803 1.794 2.555 2.589 3.747 3.761 5.722 5.495 7.728 8.061 12.025 11.862
RD/%c 0.00 0.80 1.72 0.06 1.75 0.93 0.50 1.32 0.38 3.97 4.31 1.35
a
c Standard uncertainties u are u(T) = 0.1 K, ur(p) = 0.05, ur(x1) = 0.10, and ur(w3) = 0.01. bxeq1 1 denotes the solubility calculated by eq 1. RD% = {| eq1 x1- x1 |/ x1} × 100%.
that the solubility of adipic acid reaches the maximum value at cyclohexanone mass fraction of 0.4 in the solvent mixtures, that is, the mixture of cyclohexanol and cyclohexanone with cyclohexanone mass fraction of 0.4 has the best dissolving capacity for adipic acid. This phenomenon is considered as maximum-solubility effect, which can often be seen in many systems.9,12,13 3.1.2. Solubilities of Adipic Acid in Cyclohexanone + Cyclohexane Mixtures by Titration. The solubilities of adipic acid (1) in cyclohexanone (2) + cyclohexane (3) mixtures from 303.0 to 358.0 K measured by titration analysis was listed in Table 3, where x1 is the mole fraction of solute in the mixtures and w2 is defined as the mass faction of cyclohexanone in the binary solvents. It shows that solubility of adipic acid increases with increasing temperature and mass fraction of cyclohexanone in the binary mixtures from (0.1 to 0.9) at the constant temperature. 3.1.3. Solubilities of Adipic Acid in Pure Cyclohexanol and Pure Cyclohexanone by FTIR. 3.1.3.1. Preparations of Calibration Curves and Saturations of Experimental Solutions. The solubilities of adipic acid in pure cyclohexanol (w3 = 0.0) and pure cyclohexanone (w3 = 1.0) from 303.0 to 388.8 K via in situ ATR-FTIR were evaluated by analyzing the peak areas of the CO (1800−1600 cm−1) and CO (1300− 1096 cm−1) absorption bands through a series of calibration curves. Independent IR spectra of adipic acid were collected by a “solvent subtraction” function on the iC IR 4.1 Software as shown in Figure 4. The split of CO absorption on curve II might be due to the dimer association of carboxylic acids or association hydroxyl group.3,27 A similar split occurs on the CO absorption bands. The variations of IR spectra at different experimental times after each addition of adipic acid into solvent can be plotted in a three-dimensional figure. Figure 5a,b exhibit the 3D IR spectra of CO and CO peak during addition of adipic acid into cyclohexanol, respectively. The changes of CO and CO peak area after each addition of adipic acid in cyclohexanol were presented in Figure 6a. The each step increase of peak area indicates each addition of the solute and its complete dissolution in the solvent. The calibration curves that correlate IR absorption peak areas and the added mass of adipic acid in cyclohexanol (Figure 6a) were
groups of unsaturated solutions of adipic acid in water with known concentrations were prepared and measured. The reliability was evaluated with a percent recovery of 100.0%− 101.9% at given temperatures in Table S2 in Supporting Information. This indicates that the experimental method in this work is reliable for the determination of solubility. The verification of FTIR method will be discussed in detail in Section 3.1.3.
3. RESULTS AND DISCUSSION 3.1. Solubility Data. 3.1.1. Solubilities of Adipic Acid in Cyclohexanol + Cyclohexanone Mixtures by Titration. The solubilities of adipic acid (1) in cyclohexanol (2) + cyclohexanone (3) mixtures from 303.0 to 353.0 K measured by titration analysis was listed in Table 2, where x1 was mole fraction solubility of adipic acid in cyclohexanol + cyclohexanone mixtures and w3 was defined as the mass fraction of cyclohexanone in binary solvents. It clearly shows that the solubility of adipic acid in all of the binary solvents increases with the increasing of temperature. To illustrate the effect of solvent composition on the solubility of adipic acid in the binary solvents apparently, the data in Table 2 was also plotted in Figure 3. It can be found
Figure 3. Solubilities of adipic acid (1) in cyclohexanol (2) + cyclohexanone (3) solvent mixtures: ■, T = 303.0 K; blue ●, T = 313.0 K; red ▲, T = 323.0 K; green ▼, T = 333.0 K; fuschia ◆, T = 343.0 K; ★, T = 353.0 K; , Apelblat equation calculated. C
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Table 3. Solubilities of Adipic Acid (1) in Cyclohexanone (2) + Cyclohexane (3) Mixtures at Temperature T and Pressure p = 0.1 MPaa T/K 313.0 323.0 333.0 343.0 353.0 313.0 323.0 333.0 343.0 353.0 303.0 313.0 323.0 333.0 343.0 348.0 353.0 358.0 305.2 313.0 323.0 334.0 343.0 348.0 353.7 358.0
102 x1 w2 0.020 0.034 0.045 0.055 0.079 w2 0.054 0.086 0.129 0.175 0.317 w2 0.108 0.152 0.226 0.300 0.440 0.623 0.808 1.174 w2 0.167 0.226 0.364 0.586 0.994 1.326 1.983 2.803
102 xeq1 1 = 0.1
RD/%
T/K
b
0.021 0.031 0.045 0.060 0.075 = 0.2b 0.058 0.077 0.117 0.199 0.376 = 0.3b 0.114 0.147 0.205 0.307 0.490 0.631 0.824 1.087 = 0.4b 0.171 0.224 0.342 0.600 1.010 1.380 2.002 2.682
102 x1
102 xeq1 1
RD/%
T/K
c
3.67 7.21 0.00 8.58 4.17 7.83 10.20 9.24 13.86 18.58
305.6 313.0 323.0 333.0 342.5 348.0 353.0 358.0 363.0d
4.96 3.57 9.39 2.46 11.19 1.37 1.96 7.39
303.0 313.5 323.0 333.0 343.0 348.0 354.0 358.0 363.0d 368.0d
2.47 0.83 6.02 2.45 1.65 4.06 0.98 4.30
303.0 313.0 323.0 333.0 343.0 348.0 353.0 358.0
w2 = 0.5 0.301 0.326 0.482 0.438 0.694 0.670 1.084 1.057 1.541 1.670 2.115 2.196 2.762 2.831 3.781 3.668 4.954 4.773 w2 = 0.6c 0.428 0.420 0.690 0.684 0.997 1.071 1.789 1.731 2.668 2.811 3.693 3.588 5.103 4.814 6.046 5.860 7.454 7.495 9.125 9.591 w2 = 0.7c 0.733 0.692 0.987 1.041 1.474 1.575 2.460 2.392 3.597 3.644 4.457 4.501 5.932 5.562 7.309 6.875
102 x1
102 xeq1 1
RD/%
c
8.47 9.19 3.43 2.46 8.35 3.81 2.51 2.98 3.65 1.84 0.91 7.46 3.26 5.35 2.85 5.66 3.08 0.55 5.11 5.57 5.49 6.85 2.76 1.31 0.99 6.24 5.94
363.0d 368.0d 373.0d 303.4 313.0 323.0 333.0 343.0 348.0 353.0 357.5 363.0d 368.0d 373.0d 378.5d 303.0 313.0 323.0 333.0 343.0 347.5 352.0 357.3 363.0d 368.6d 373.0d 378.5d
w2 = 0.7 8.564 8.498 10.010 10.506 12.635 12.988 w2 = 0.8c 1.055 1.032 1.553 1.574 2.387 2.403 3.421 3.610 5.339 5.342 6.639 6.465 8.039 7.798 9.631 9.205 11.368 11.236 12.949 13.426 15.296 15.995 19.714 19.330 w2 = 0.9c 1.500 1.468 2.245 2.231 3.153 3.327 4.762 4.877 6.931 7.034 8.447 8.253 10.112 9.656 12.205 11.575 14.167 14.008 16.070 16.827 18.552 19.382 23.528 23.052
0.77 4.96 2.80 2.16 1.38 0.67 5.51 0.06 2.62 3.00 4.42 1.16 3.68 4.57 1.95 2.14 0.63 5.52 2.41 1.48 2.29 4.51 5.16 1.12 4.71 4.47 2.02
a
Standard uncertainties u are u(T) = 0.1 K and ur(p) = 0.05. bAcquired by a titration analysis, and relative standard uncertainty is ur(x1) = 0.10. Acquired by a titration analysis except superscript d, and relative standard uncertainty is ur(x1) = 0.10. dAcquired by a FTIR method, and relative standard uncertainty is ur(x1) = 0.10. c
were displayed in Figure 7. After an excess addition of adipic acid, a maximum value (As) of IR absorption peak area was obtained, and then could be substituted in the related calibration curve (in Figure 6b) to calculate the saturation concentration of adipic acid in solvent at given temperature, corresponding to the extrapolating value from the related calibration curve according to the maximum value (As). The saturation concentration of adipic acid in solvent at given temperature can be calculated simultaneously from the maximum CO and CO absorption peak areas (As‑I and As‑II in Figure 7). To acquire the solubility of adipic acid in different solvents under different temperatures, similar experiments were carried out under temperatures range of 304.2 to 388.0 K in cyclohexanol, and of 303.5 to 388.8 K in cyclohexanone, respectively. The added masses of adipic acid for each calibration curve at given temperature were included in Table S3 in Supporting Information. The related regression equations for these calibration curves were concluded in Table S4 in Supporting Information with all correlation coefficients higher than 0.99. According to the Beer−Lambert law, a linear relationship can be obtained at lower concentration and a deviation might occur resulting from the changes in absorptivity coefficients or refractive index at high analyte concentration.29 In this work, a quadratic polynomial equation was applied in a
Figure 4. IR spectra of adipic acid in different solvents (10 g/50 g) after subtracting the solvents absorptions: I, in cyclohexanol at 363.0 K; II, in cyclohexanone at 376.0 K.
displayed in Figure 6b. A good linear relationship was obtained with linear correlation coefficients higher than 0.99. All the results shown in Figure 5 and 6 were collected before the saturation of the experimental solution. No change of IR absorption peak area formed after the addition of adipic acid means that the concentration of adipic acid in solvents reaches a maximum value, and the saturation state of adipic acid in solvents can be achieved. The observation and estimation of the saturation concentration of adipic acid D
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Figure 5. Three-dimensional plots during addition of adipic acid into cyclohexanol at 358.2 K. (a) CO absorption. (b) CO absorption.
Figure 6. (a) Relationship between IR peak areas and added masses of adipic acid in cyclohexanol at 358.2 K: I, CO peak areas; II, CO peak areas. (b) Calibration curves for CO (1800−1600 cm−1) and CO (1300−1096 cm−1) absorption bands in cyclohexanol at 358.2 K: blue □, CO; I, y = 6.3610 + 3.1270x, r2 = 0.9941; red ○, CO; II, y = 5.9630 + 3.6743x, r2 = 0.9977.
acquired by in situ ART-FTIR method. Both solubility values calculated on the basis of CO and CO absorption peak area agreed well with each other with an averaged relative deviation (ARD1) less than 1.0%. Also Table 4 lists the comparison of solubility data obtained by the in situ ATR-FTIR method and the titration analysis. A very good agreement between the values obtained by the two methods was observed with the averaged relative deviation (ARD2) less than 2.0% at given temperatures. The good consistency indicates that the in situ ATR-FTIR method can be applied to acquire reliable and accurate solubility curves without any sampling operation, especially at higher temperatures. Furthermore, the data in Table 4 was compared to those reported in literatures by other methods.5,6 As plotted in Figure 8, both the solubilities of adipic acid in pure cyclohexanol and pure cyclohexanone are in agreement with the data acquired by laser detecting system (ref 5) and by sampling and HPLC analysis (ref 6) under lower temperature ( 0, ΔsolG° > 0) and entropy-driving (ΔsolH° > 0, ΔsolS° > 0). Furthermore, enthalpy is the main contributor to the Gibbs free energy of both two dissolution processes, because all values of ζH% are ≥54.68% in cyclohexanol + cyclohexanone mixtures and ≥55.93% in cyclohexanone + cyclohexane mixtures, respectively.
4. CONCLUSIONS The solubilities of adipic acid in cyclohexanol + cyclohexanone mixtures from 303.0 to 353.0 K and in cyclohexanone + cyclohexane mixtures from 303.0 to 378.5 K were determined by a titration and an in situ ATR-FTIR method. The solubility increases with the increase of temperature and with the increasing mass fraction of cyclohexanone in cyclohexanone + cyclohexane mixtures from (0.1 to 0.9) at constant temperature. However, the solubility of adipic acid in cyclohexanol + cyclohexanone mixtures reaches the maximum at cyclohexanone mass fraction of 0.4.
Figure 10. van’t Hoff plots of lnx1 versus 1/T in cyclohexanol (2) + cyclohexanone (3) solvent mixtures from 303.0 to 388.8 K: red +, w3 = 0.0; green ●, w3 = 0.2; fuschia ◆, w3 = 0.4; red ★, w3 = 0.6; blue ▲, w3 = 0.8; red ×, w3 = 1.0; solid symbols, titration determined; green △, w3 = 0.0; green □, w3 = 1.0; open symbols, FTIR determined. H
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21.75 34.53 36.85 41.56 42.14 43.26 43.29 43.88 44.07
Also, the solubilities of adipic acid in pure cyclohexanol and pure cyclohexanone from 303.0 to 388.8 K were acquired by the FTIR method, respectively. Herein, by the verification of titration, a good agreement between the values obtained by the two methods was observed with the averaged relative deviation (ARD2) less than 2.0% at given temperatures, which indicates that the solubilities obtained herein are reliable and accurate at given temperatures. Apelblat equation and λh equation were well employed to correlate the experimental data. In addition, van’t Hoff equation was applied to determine the thermodynamics functions of the dissolution process, including the enthalpy, entropy, and Gibbs free energy. The results show that both of the dissolution processes of adipic acid in cyclohexanol + cyclohexanone mixtures and in cyclohexanone + cyclohexane mixtures are endothermic and entropy-driving. The experimental solubilities in this work are reliable and can be used as essential data for the synthetic and crystallization process of adipic acid.
21.49 18.40 15.58 13.76 11.72 10.65 9.35 8.13 7.39 24.90 61.76 65.52 101.45 92.65 101.50 88.21 84.58 79.60
78.25 65.47 63.15 58.44 57.86 56.74 56.71 56.12 55.93
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ASSOCIATED CONTENT
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AUTHOR INFORMATION
Corresponding Author
Raw solubility data acquired by FTIR in Table 4. bRaw solubility data acquired by titration in Table 2.
29.76 38.93 37.41 47.62 43.16 44.81 39.52 37.30 34.82 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 45.32 43.81 43.07 43.52 43.24 43.14 42.86 44.92 54.68 56.19 56.93 56.48 56.76 56.86 57.14 55.08 5.71 7.46 6.50 6.23 6.72 7.18 8.39 6.46 78.91 80.77 61.68 63.93 65.76 69.10 76.99 81.47 33.35 33.88 26.67 27.14 28.23 29.79 33.57 35.03 0.0 0.0b 0.2b 0.4b 0.6b 0.8b 1.0b 1.0a
a
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.5b00880. Experimental details and calibration curve equations for in situ ATR-FTIR method. (PDF)
*E-mail:
[email protected]. Tel. and fax: +86 57187951227. Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors gratefully acknowledge United State Key Laboratory of Chemical Engineering at Zhejiang University (Grant No. SKL/ChE-09Z02) for financial supports.
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REFERENCES
(1) Weissermel, K.; Arpe, H. Industrial Organic Chemistry; VCH Verlagsgesellschaft mbH: Weinheim, 1997. (2) Myers, R. L. The 100 Most Important Chemical Compounds: A Reference Guide; Greenwood Press: London, 2007. (3) Silva, A. D. P. M.; Silva, J. F. C. Determination of the Adipic Acid Solubility Curve in Acetone by Using ATR-FTIR and Heat Flow Calorimetry. Org. Process Res. Dev. 2011, 15, 893−897. (4) Li, Y.; Wang, Y.; Ning, Z.; Cui, J.; Wu, Q.; Wang, X. Solubilities of Adipic Acid and Succinic Acid in a Glutaric Acid + Acetone or nButanol Mixture. J. Chem. Eng. Data 2014, 59, 4062−4069. (5) Fan, L.; Ma, P.; Xiang, Z. Measurement and correlation for solubility of adipic acid in several solvents. Chin. J. Chem. Eng. 2007, 15, 110−114. (6) Suren, S.; Sunsandee, N.; Stolcova, M.; Hronec, M.; Leepipatpiboon, N.; Pancharoen, U.; Kheawhom, S. Measurement on the solubility of adipic acid in various solvents at high temperature and its thermodynamics parameters. Fluid Phase Equilib. 2013, 360, 332−337. (7) Mao, Z.; Sun, X.; Luan, X.; Wang, Y.; Liu, G. Measurement and Correlation of Solubilities of Adipic Acid in Different Solvents. Chin. J. Chem. Eng. 2009, 17, 473−477. (8) Wei, D.; Cao, W. Solubility of Adipic Acid in Acetone, Chloroform, and Toluene. J. Chem. Eng. Data 2009, 54, 152−153.
a
ζS% ζH% Δsol G°/(kJ·mol−1) Δsol S°/(J·mol−1·K−1) Δsol H°/ (kJ·mol−1)
in cyclohexanone (2) + cyclohexane (3) mixtures
Article
S Supporting Information *
w2 ζS% ζH% Δsol G°/(kJ·mol−1) Δsol S°/(J·mol−1·K−1)
in cyclohexanol (2) + cyclohexanone (3) mixtures
Δsol H°/(kJ·mol−1) w3
Table 7. Thermodynamic Functions of Dissolution of Adipic Acid (1) in Cyclohexanol (2) + Cyclohexanone (3) Mixtures and Adipic Acid (1) in Cyclohexanone (2) + Cyclohexane (3) Mixtures
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DOI: 10.1021/acs.jced.5b00880 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
