Solubility Determination, Modeling, and Preferential Solvation of

Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Solubility Determination, Modeling, and Preferential Solvation of Terephthalaldehydic Acid Dissolvend in Aqueous Solvent Mixtures of Methanol, Ethanol, Isopropanol, and N‑Methyl-2-pyrrolidone Jinhua Liang, Jiaojiao Ma, Jingchao Han, Min Zheng, and Hongkun Zhao* College of Chemistry & Chemical Engineering, YangZhou University, YangZhou, Jiangsu 225002, People’s Republic of China

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S Supporting Information *

ABSTRACT: The present work mainly reports the terephthalaldehydic acid solubility in aqueous solutions of methanol, ethanol, isopropanol, and NMP, which was achieved through a steady-state method covering a temperature range from 283.15 to 323.15 K under 101.1 kPa. The terephthalaldehydic acid solubility increased positively as the mass fraction of methanol (ethanol, isopropanol, and NMP) increased for the investigated mixtures of methanol (ethanol, isopropanol, and NMP) and water. At the same temperature and mass fraction of methanol (ethanol, isopropanol, and NMP), the mole fraction solubility of terephthalaldehydic acid was higher in the NMP and water mixture than in the other three mixtures. The solid equilibrating with saturated liquor was indentified through Xray power diffraction, which showed no crystal transition, polymorphic transformation, or solvate formation. Three models, the Van’t Hoff−Jouyban− Acree, Jouyban−Acree, and Apelblat−Jouyban−Acree, were used here to correlate the obtained solubility data. The back-calculated values were in good agreement with the determined ones. The values of RAD and RMSD were, respectively, no greater than 3.63% and 6.66 × 10−4. Preferential solvation of terephthalaldehydic acid in the four mixtures was analyzed by employing the method of inverse Kirkwood−Buff integrals. The preferential solvation parameter δx1,3 by NMP (methanol, ethanol, or isopropanol; 1) is positive within the composition range of 0.16 < x1 < 1 for NMP, 0.32 < x1 < 1 for methanol, and 0.25 < x1 < 1 for ethanol and isopropanol. As it can be speculated that in the regions where terephthalaldehydic acid is preferentially solvated by NMP (methanol, ethanol, or isopropanol), terephthalaldehydic acid acts as a Lewis acid with NMP (methanol, ethanol, or isopropanol) molecules.

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INTRODUCTION Terephthalic acid is a significant aromatic compound. It can be widely employed in many organic syntheses, especially in polyester fields.1−4 During the terephthalic acid production through p-xylene oxidation, a lot of byproducts are generated. Terephthalaldehydic acid (CAS Reg. No. 619-66-9; chemical structure, Figure 1) is a main byproduct.5−9 Crystallization in a

solubility in diverse solvents and solvent mixtures is desirable, which may affect the purity, yield, and crystal size distribution of the product. Therefore, accurate solubility data are necessary in designing the crystallization process and carrying out supplementary thermodynamic investigation.11,12 The solubility of terephthalaldehydic acid in some neat solvents is available in previous publications;13−19 however, the physicochemical property of terephthalaldehydic acid in mixed solvents has not yet been studied. The prediction of solid solubility in solvent mixtures can be performed through several theoretical and semiempirical models. On the other hand, the experimental solubility data are very essential for chemical and pharmaceutical scientists.20 It is common knowledge that solvent mixtures with temperature adjustment are a customary method to alter the solid solubility in crystallization investigations. The knowledge of solubility facilitates us to discover the most suitable solvents or solvent mixtures in separating terephthalaldehydic acid by using the crystallization method. A literature review shows that the solubility of terephthalaldehydic acid in neat water is low.15−17

Figure 1. Chemical structure of terephthalaldehydic acid.

solvent is an important operation unit to separate mixtures, where the solid−liquid phase equilibrium is of great importance in choosing and designing a solvent crystallization technique. This separation method has been used in terephthalic acid purification at present.10 To purify terephthalic acid by separating terephthalaldehydic acid from the mixture, knowledge of comprehensive and systemic terephthalaldehydic acid © XXXX American Chemical Society

Received: December 30, 2018 Accepted: February 27, 2019

A

DOI: 10.1021/acs.jced.8b01262 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Detailed Information of Terephthalaldehydic Acid and the Selected Solvents chemicals terephthalaldehydic acid ethanol isopropanol NMP methanol water

initial mass fraction purity

final mass fraction purity

purification method

Sigma Chemical Co., Ltd.

0.988

0.997

recrystallization

HPLCa

Sinopharm Chemical Reagent Co., Ltd., China

0.994 0.995 0.995 0.994

none none none none distillation

GCb GC GC GC conductivity meter

molar mass g·mol−1 150.13 46.07 60.01 99.13 32.04 18.02

source

0.994 0.995 0.995 0.994 conductivity < 2 μS·cm−1

our lab

analytical method

a

High-performance liquid chromatography. bGas chromatography.

The solvent mixures can alter the solubility of terephthalaldehydic acid. With the intention of providing essential data in engineering fields and more useful thermodynamic information upon terephthalaldehydic acid crystallization from mixed solvents, the main aims of the work are to (1) measure the terephthalaldehydic acid solubility in methanol and water, ethanol and water, isopropanol and water, and NMP and water mixtures with different solvent compositions; (2) describe mathematically the experimental solubility through the Jouyban−Acree model,12,20−22 Van’t Hoff−Jouyban−Acree model,20−22 and Apelblat−Jouyban−Acree model;21,22 and (3) discuss the respective thermodynamic quantities of the solvent mixures. In addition, the boiling point of methanol is 337.9 K; in order to compare the obtained solubility data, the temperature range of 283.15 to 323.15 K for solubilities is selected.

Figure 2. Schematic diagram of experimental apparatus: I, smart thermostatic water bath; II, mercury-in-glass thermometer; III, magnetic stirrer; IV, stirrer controller; V, jacketed glass vessel; VI, sampling port; VII, condenser.

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EXPERIMENTAL SECTION Materials and Apparatus. The purchased terephthalaldehydic acid from Sigma Chemical Co., Ltd., China had a mass fraction of 0.988. The purification process was carried out via recrystallization in ethanol. The final purity of terephthalaldehydic acid used in experiment was 0.997 in the mass fraction, which was determined by using an Agilent 1260 HPLC (highperformance liquid chromatography). The analytical grade organic solvents (isopropanol, ethanol, methanol, and NMP) had a mass fraction purity of no less than 0.994, which was analyzed by using a gas chromatograph (FULI 9790, China). The detailed aspects of the chemicals used here are listed in Table 1. Preparation of Binary Solvent Mixtures. The solvent mixures used here were prepared by using an analytical balance, model BSA224S. The amount of solvent mixture employed in each experiment was around 60 mL, the standard uncertainty of which was assessed to be 0.0001 g. The mass fractions of ethanol (methanol, isopropanol, and NMP) in ethanol (methanol, isopropanol, and NMP; 1) and water (2) solutions covered the composition range from 0 to 1. Experimental Apparatus and Procedure. The apparatus diagram for solubility measurement and the determination process were similar to those used in our previous works.22−24 The apparatus is given in Figure 2. It comprised a 100 mL jacketed glass vessel, a magnetic stirrer, and a circulating water system, the temperature having been controlled by using a thermostatic water bath (QYHX-1030; standard uncertainty: 0.05 K) provided by Shanghai Joyn Electronic Co., Ltd., China. The reliability of the experiment apparatus was confirmed by measuring benzoic acid solubility in neat toluene.23,24

The terephthalaldehydic acid solubility in methanol and water, ethanol and water, isopropanol and water, and NMP and water mixtures was determined by using the technique of isothermal dissolution equilibrium.22−24 The saturated solutions of terephthalaldehydic acid were gained in a glass vessel. An excessive amount of terephthalaldehydic acid was introduced into about 60 mL of solvent mixtures. Around 0.5 mL of the liquid phase was withdrawn at intervials of 1 h and analyzed by using the HPLC. If the composition of liquor did not vary, the mixture system was supposed to be in equilibrium. Results showed that 9 h was enough for all investigated solvent mixtures. Then, the stirring was stopped for 30 min. The clear upper liquor was taken out and transferred instantly into a preweighed volumetric flask. Finally, the sample was diluted with neat methanol, and 1 μL was taken out for analysis. A highperformance liquid chromatograph (HPLC) with an inverse column was used to determine the solubility of terephthalaldehydic acid.15 The local ambient pressure was about 101.1 kPa in the experiment. The terephthalaldehydic acid solubility in a mole fraction (xw,T) in the selected solutions can be obtained through eq 1. Furthermore, the initial composition of mixtures (w) is evaluated by using eqs 2 and 3. x w,T =

m1/M1 m1/M1 + m2 /M 2 + m3 /M3

w1 = w = B

m2 m 2 + m3

(1)

(2) DOI: 10.1021/acs.jced.8b01262 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data w2 =

m3 m 2 + m3

Article

is found in pure methanol (ethanol, isopropanol, and NMP) for the methanol (ethanol, isopropanol, and NMP) and water mixtures. It can also be elucidated from Tables 2−5 that the terephthalaldehydic acid solubility in NMP and water is higher than that in ethanol and water, methanol and water, and isopropanol and water at the same composition of ethanol (methanol, isopropanol, and NMP) and temperature. The mole fraction solubility of terephthalaldehydic acid is observed to near a 102 to 103-fold rise in going from neat water to ethanol (methanol, isopropanol, and NMP). For the systems of terephthalaldehydic acid and alcohol, the solubility value shows agreement with the varying trend of solvent polarity except for isopropanol. The structure of terephthalaldehydic acid is approximately symmetrical, so it has relatively small polarity. The polarity of the water and methanol mixture is greater than that of the water and ethanol mixture at a given composition of alcohol, so the terephthalaldehydic acid solubility in the water and ethanol mixture is smaller than that in the water and methanol mixture. On the other hand, terephthalaldehydic acid has high dipole moments. As a result, it can present strong dipole−dipole interactions with NMP due to its −COOH group. The formation of H-bonds has a significant effect upon the terephthalaldehydic acid solubility. The terephthalaldehydic acid solubility is higher in NMP than in the other studied solvent mixtures. Clearly, this case is due to the formation of H-bonds between the −COOH group of terephthalaldehydic acid and the free electron pairs of the oxygen atom and nitrogen atom of NMP. The solubilities in neat water and NMP obtained in the present work as well as those reported in the previous publications13,15−19 are shown in Figure 5 for comparison. In addition, the solubility data are presented in Tables S1 and S2 of the Supporting Information. It may be observed that, if the reported solubility data are extrapolated to relatively lower temperatures, then the solubility values in NMP determined by us are lower than those reported by Wang and co-workers.18 The discrepancies increase with increasing temperature. As described by Wang and co-workers, the solute and NMP are preweighed and introduced to a jacketed vessel with an internal volume of about 20 cm3. The solvent NMP is easy to volatilize. Even if a condenser is used during the experimental process, lots of solvent remains in the condenser. Additionally, the jacketed vessel is not full of liquor, and a liquid−gas equilibrium of the solvent is attained in it. A lot of solvent exists in the gas phase. The higher the temperature is, the more solvent exists in the gas phase and condenser. However, Wang and co-workers ignore the loss of solvent, especially at higher temperatures. Consequently, the determined solubility by Wang et al. is higher than the real value. The discrepancy increases with the increase in temperature. In the present work, the solubility measurement is carried out by using the steady-state technique at a relatively low temperature; the solvent evaporation has little influence upon the determinated solubility. The obtained solubilities in the solvents water and NMP by us are consistent with those reported in the publications.13,15−19 Thermodynamic Modeling. Here, three cosolvency models are used to express mathematically the terephthalaldehydic acid solubility in mixtures of methanol and water, ethanol and water, isopropanol and water, and NMP and water at various temperatures, which are the Jouyban−Acree model,12,20−22 Van’t Hoff−Jouyban−Acree model,20−22 and Apelblat−Jouyban−Acree model.21,22

(3)

where m1 refers to the mass of terephthalaldehydic acid; m2 stands for the mass of isopropanol, methanol, ethanol, or NMP; and m3 stands for the mass of water. M1, M2, and M3 refer to the corresponding molar masses. The relative standard uncertainty is 4.4% for the mole fraction solubility. X-Ray Powder Diffraction. So as to determine the presence of solvation or polymorph transformation of terephthalaldehydic acid during the experiment, the solid equilibrated with liquid was collected and tested by using XRD (X-ray powder diffraction). The analysis was carried out on a HaoYuan DX2700B instrument at ambient temperature. The Cu Kα radiation was set to 1.54184 nm at a speed of 6 deg·min−1. The tube voltage and current were, respectively, 40 kV and 30 mA. The data determined were gathered within the range from 10° to 80° (2Θ).

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RESULTS AND DISCUSSION XRD Analysis. The XRD patterns of the raw terephthalaldehydic acid and the solid equilibrated with liquor in solvent mixures are shown in Figure 3. It may be found that all XRD

Figure 3. XRD patterns of terephthalaldehydic acid: (a) raw material; (b) equilibrated with methanol; (c) equilibrated with ethanol; (d) equilibrated with isopropanol; (e) equilibrated with NMP; (f) equilibrated with water; (g) equilibrated with methanol (1) + water (2) mixture; (h) equilibrated with ethanol (1) + water (2) mixture; (i) equilibrated with isopropanol (1) + water (2) mixture; (j) equilibrated with NMP (1) + water (2) mixture.

patterns of solid phases equilibrated with their equilibrium liquid have the same characteristic peaks with raw material terephthalaldehydic acid. As a result, there is no solvate formation or polymorph transformation in the experiment. Experimental Solubility. The mole fraction solubility of terephthalaldehydic acid in mixtures of methanol (1) + water (2), ethanol (1) + water (2), isopropanol (1) + water (2), and NMP (1) + water (2) are, respectively, presented in Tables 2, 3, 4, and 5, and plotted in Figure 4. Tables 2−5 show that the terephthalaldehydic acid solubility is a function of solvent temperature and composition for the all solvent mixtures. It rises with an increase in temperature and mass fraction of isopropanol (ethanol, methanol, and NMP). The maximum solubility value C



Article

Table 2. Experimental Mole Fraction Solubility (xeT,W × 104) of Terephthalaldehydic Acid in Mixed Solvent of NMP (w) + Water (1 − w) with Various Mass Fractions within the Temperature Range from T/K = 283.15 to 323.15 under p = 101.1 kPaa w T/K

0.0000

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1.000

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.2146 0.2827 0.3615 0.4645 0.5906 0.7670 0.9572 1.200 1.482

0.8103 1.030 1.286 1.644 2.137 2.689 3.300 3.985 4.851

2.137 2.667 3.400 4.236 5.289 6.479 7.925 9.626 11.90

4.543 5.486 6.845 8.540 10.40 12.45 15.16 18.01 21.13

9.898 12.35 14.91 18.45 21.74 26.47 31.18 36.44 42.93

21.92 25.82 31.18 37.65 45.09 54.45 63.10 73.14 84.07

38.59 46.21 56.26 66.83 80.69 93.52 108.4 129.8 151.7

78.73 92.76 107.5 128.8 154.2 183.2 210.5 246.0 289.8

150.4 180.2 215.8 248.0 294.6 341.5 395.8 462.5 527.3

322.4 383.0 458.7 536.0 626.3 731.9 834.4 943.6 1090

653.9 767.4 896.7 1044 1210 1397 1607 1843 2106

a

Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.044. Solvent mixtures were prepared by mixing different masses of the solvents with relative standard uncertainty ur(w) = 0.0002. w represents the mass fraction of NMP in mixed solvents of NMP (w) + water (1 − w) free of terephthalaldehydic acid.

Table 3. Experimental Mole Fraction Solubility (xeT,W × 104) of Terephthalaldehydic Acid in Mixed Solvent of Methanol (w) + Water (1 − w) with Various Mass Fractions within the Temperature Range from T/K = 283.15 to 323.15 under p = 101.1 kPaa w T/K

0.0000

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1.000

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.2146 0.2827 0.3615 0.4645 0.5906 0.7670 0.9572 1.200 1.482

0.3891 0.5123 0.6660 0.8413 1.076 1.334 1.675 2.090 2.591

0.5962 0.7766 0.9750 1.254 1.556 1.941 2.407 3.022 3.679

0.9506 1.206 1.520 1.905 2.374 2.942 3.628 4.451 5.435

1.848 2.263 2.859 3.589 4.424 5.452 6.533 7.997 9.467

3.130 3.806 4.618 5.592 6.758 8.150 9.809 11.80 14.10

6.808 8.081 9.593 11.41 13.50 16.01 19.01 22.50 26.71

15.81 18.30 21.21 24.70 28.61 33.50 39.01 45.60 53.41

32.81 38.80 45.11 51.40 58.71 67.30 77.51 89.30 100.4

55.00 64.11 71.10 81.30 92.11 104.4 117.9 134.4 149.2

78.10 89.91 99.91 115.0 128.5 144.4 163.3 178.0 200.1

a

Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.044. Solvent mixtures were prepared by mixing different masses of the solvents with relative standard uncertainty ur(w) = 0.0002. w represents the mass fraction of methanol in mixed solvents of methanol (w) + water (1 − w) free of terephthalaldehydic acid.

Table 4. Experimental Mole Fraction Solubility (xeT,W × 104) of Terephthalaldehydic Acid in Mixed Solvents of Ethanol (w) + Water (1 − w) with Various Mass Fractions within the Temperature Range from T/K = 283.15 to 323.15 under p = 101.1 kPaa w T/K

0.0000

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1.000

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.2146 0.2827 0.3615 0.4645 0.5906 0.7670 0.9572 1.200 1.482

0.3325 0.4183 0.5545 0.6885 0.895 1.118 1.407 1.747 2.212

0.6448 0.8272 1.048 1.344 1.669 2.058 2.589 3.215 3.991

1.234 1.594 1.979 2.506 3.152 3.939 4.748 5.848 7.156

2.705 3.396 4.264 5.320 6.721 8.441 10.20 12.50 14.90

5.860 7.276 8.982 11.11 13.50 16.41 19.80 23.81 28.60

10.89 13.25 16.03 19.64 23.44 28.35 34.07 41.00 48.20

19.31 23.20 27.91 33.40 39.91 47.60 56.61 66.90 79.01

30.30 36.10 44.00 52.17 64.80 75.71 89.50 104.1 120.4

47.81 57.61 67.80 81.49 98.10 115.9 135.7 158.6 182.7

81.49 97.28 115.5 133.6 155.3 181.1 210.9 246.1 280.5

a Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.044. Solvent mixtures were prepared by mixing different masses of the solvents with relative standard uncertainty ur(w) = 0.0002. w represents the mass fraction of ethanol in mixed solvents of ethanol (w) + water (1 − w) free of terephthalaldehydic acid.

where xw,T signifies the terephthalaldehydic acid solubility in mole fraction in solvent mixtures at absolute temperature T; w1 and w2 denote the mass fraction of solvents 1 (isopropanol, methanol, ethanol, and NMP) and 2 (water) free of terephthalaldehydic acid, respectively; and x1,T and x2,T are the terephthalaldehydic acid solubilities in mole fraction in neat solvents. The Jouyban−Acree model parameters are denoted as Ji.

The Jouyban−Acree model expressed as eq 4 provides an accurate mathematical description for solute solubility dependence upon both solvent composition and temperature for solvent mixures.12,20−22 ln x w,T = w1 ln x1,T + w2 ln x 2,T +

w1w2 T /K

2

∑ Ji (w1 − w2)i i=0

(4) D



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Table 5. Experimental Mole Fraction Solubility (xeT,W × 104) of Terephthalaldehydic Acid in Mixed Solvents of Isopropanol (w) + Water (1 − w) with Various Mass Fractions within the Temperature Range from T/K = 283.15 to 323.15 under p = 101.1 kPaa w T/K

0.0000

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1.000

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.2146 0.2827 0.3615 0.4645 0.5906 0.7670 0.9572 1.200 1.482

0.4073 0.5305 0.6910 0.8946 1.144 1.445 1.803 2.277 2.756

0.8321 1.094 1.413 1.802 2.291 2.883 3.592 4.454 5.475

1.576 2.034 2.593 3.283 4.123 5.139 6.359 7.814 9.538

3.159 4.011 5.052 6.316 7.841 9.669 11.90 14.40 17.50

5.904 7.395 9.202 11.40 14.00 17.10 20.70 25.01 30.10

10.31 13.10 16.11 19.30 23.51 28.30 34.31 40.50 48.90

15.20 19.11 23.30 28.90 34.11 40.90 49.21 59.80 69.71

23.20 28.01 34.50 42.01 50.20 60.01 72.50 83.11 98.40

34.80 43.31 52.70 63.01 75.31 88.90 103.7 119.4 139.9

49.81 61.20 72.71 86.70 102.6 120.7 139.9 163.2 184.6

a

Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.044. Solvent mixtures were prepared by mixing different masses of the solvents with relative standard uncertainty ur(w) = 0.0002. w represents the mass fraction of isopropanol in mixed solvents of isopropanol (w) + water (1 − w) free of terephthalaldehydic acid.

Figure 4. Mole fraction solubility (x) of terephthalaldehydic acid in (a) NMP (w) and water (1 − w), (b) methanol (w) and water (1 − w), (c) ethanol (w) and water (1 − w), and (d) isopropanol (w) and water (1 − w) mixed solutions with various mass fractions at different temperatures: w, mass fraction of methanol (NMP, ethanol, or isopropanol); ■, w = 0; ●, w = 0.1000; ▲, w = 0.2000; ⧫, w = 0.3000; ▼, w = 0.4000; ★, w = 0.5000; △, w = 0.6000; ○, w = 0.7000; ☆, w = 0.8000; ◀, w = 0.9000; □, w = 1. , calculated curves by the Jouyban−Acree model.

i i B1 yz B2 yz zz + w2jjjA 2 + zz ln x w,T = w1jjjjA1 + z j T /K { T /K z{ k k 2 ww + 1 2 ∑ Ji (w1 − w2)i T /K i = 0

The Van’t Hoff equation is ideal, which describes the dependence of the natural logarithm of mole fraction solubility upon the reciprocal of temperature.25 ln x T = A +

B T /K

(6)

(5)

Through introducing eq 5 into eq 4, the Van’t Hoff−Jouyban−

A1, B1, A2, B2, and Ji denote parameters. The Apelblat equation given as eq 7 is a semiempirical

Acree model is obtained as eq 6.20−22

equation including three parameters A, B, and C. E



Article

Figure 5. Comparison of the mole fraction solubility (x) of terephthalaldehydic acid in water and NMP at different temperatures. (a) water: ■, ref 16; ●, ref 15; ▲, ref 17; ▼, this work. (b) NMP: ■, ref 16; ●, ref 13; ▲, ref 18; ▼, this work.

ln x T = A +

B + C ln(T /K ) T /K

relatively low. As a result, the three models may be used to describe the terephthalaldehydic acid solubility in the four solvent mixtures, and the Jouyban−Acree model provides a better correlation result. These cosolvency solubility models have been used to correlate solubility data of many solids dissolved in solvent mixtures, e.g., paclobutrazol22 and dehydroepiandrosterone acetate.24 The obtained RAD values usually do not exceed 5%. So the correlation results provide good agreement with the experimental ones. Preferential Solvation of Terephthalaldehydic Acid. As discussed above, terephthalaldehydic acid solubility shows a near 102 to 103-fold increase on going from neat water to the solvent NMP (ethanol, methanol, and isopropanol). The significant increase in solubility suggests the existence of preferential solvation of terephthalaldehydic acid in the mixtures.26 The method of inverse Kirkwood−Buff integrals (IKBI) describes the local compositions nearby a solute with respect to diverse components existing in the solvent mixtures. This dealing depends on the values of standard molar Gibbs energies of transfer of solute (compound 3) from pure water (compound 2) to the mixed solvents of solvent (compound 1) and water (compound 2) and the excess molar Gibbs energy of mixing for the solute-free mixtures. As a result, this treatment is of great importance in pharmaceutical and chemical sciences to apprehend the molecular solute−solvent interactions. The general equation of the inverse Kirkwood−Buff integral is expressed as

(7)

By substituting eq 7 into eq 4, the Apelblat−Jouyban−Acree model is derived as21,22 ÄÅ ÉÑ ÅÅ ÑÑ B1 Å + C1 ln(T /K )ÑÑÑ ln x w,T = w1ÅÅA1 + ÅÅÇ ÑÑÖ T /K ÄÅ ÉÑ ÅÅ ÑÑ B2 + w2ÅÅÅA 2 + + C2 ln(T /K )ÑÑÑ ÅÅÇ ÑÑÖ T /K 2 ww + 1 2 ∑ Ji (w1 − w2)i T /K i = 0 (8) The determined solubility data of terephthalaldehydic acid dissolved in the selected solvent mixtures are correlated with eqs 4, 6, and 8. The employed objective function is expressed as F=

∑ (ln xie − ln xic)2 i=1

(9)

Furthermore, the relative average deviation (RAD) and rootmean-square deviation (RMSD) are also used to evaluate the three models. RAD =

1 N

c e ij |x w,T − x w,T | yzz zz e z x w,T k {

∑ jjjj

(10)

N

RMSD =

c e ∑i = 1 (x w,T )2 − x w,T

N

Gi ,3 =

(11)

xew,T

Here, N denotes the number of experimental data points. refers to the experimental value and xcw,T, the computed one. According to the determined solubility, the parameters in eqs 4, 6, and 8 are acquired with the Mathcad software. The regressed parameters’ values are present in Table 6 as well as the RAD and RMSD values. The back-calculated terephthalaldehydic acid solubility in methanol and water, ethanol and water, isopropanol and water, and NMP and water mixtures with the Jouyban−Acree model are plotted in Figure 4. As is shown in Table 6 for the selected solvent mixtures, the maximum RAD value is 3.63%, which is obtained by using the van’t Hoff− Jouyban−Acree and Apelblat−Jouyban−Acree models for the methanol and water mixture. In addition, the values of RMSD are all no greater than 6.66 × 10−4. On the whole, the values of RAD and RMSD attained with the Jouyban−Acree model are

∫0

rcor

(gi ,3 − 1)4πr 2 dr

(12)

In eq 12, gi,3 is the pair correlation function for solvent i molecules in solvent (1) and water (2) mixtures around the terephthalaldehydic acid (3). r refers to the distance between the centers of terephthalaldehydic acid (3) molecules and that of solvent (1) or water (2), and rcor is the correlation distance for which gi,3 (r > rcor) is approximately equal to 1. Therefore, for all distances r > rcor up to infinity, the integral value is essentially 0. In binary mixtures of methanol and water, NMP and water, ethanol and water, and isopropanol and water, the parameter of preferential solvation of terephthalaldehydic acid (compound 3) by the solvent (1) in solvent (1) and water (2) mixtures is expressed as27−31 L δx1,3 = x1,3 − x1 = −δx 2,3

F



Article

Table 6. Values of Parameters Acquired Using the Solubility Models Jouyban−Acree parameter J0 J1 J2

RAD × 102 RMSD × 104

541.1 −770.1 531.2

parameter NMP + water A1 B1 A2 B2 J0 J1 J2

3.17 6.65 J0 J1 J2

RAD × 102 RMSD × 104

−238.1 547.0 1099

RAD × 102 RMSD × 104

337.2 760.6 −1288

methanol + water A1 B1 A2 B2 J0 J1 J2

662.9 260.5 −636.2

parameter

value

6.764 −2680 4.949 −4448 542.0 −770.2 533.6

A1 B1 C1 A2 B2 C2 J0 J1 J2

−18.20 −1553 3.713 8.698 −4620 −0.5568 541.9 −771.4 533.2 3.26 6.65

A1 B1 C1 A2 B2 C2 J0 J1 J2

4.204 −2212 −0.2205 8.698 −4620 −0.5568 −237.5 545.3 1100 3.63 2.08

A1 B1 C1 A2 B2 C2 J0 J1 J2

−34.50 −1033 5.906 8.698 −4620 −0.5568 370.2 503.6 −777.8 1.95 0.85

A1 B1 C1 A2 B2 C2 J0 J1 J2

84.82 −6586 −11.84 8.698 −4620 −0.5568 693.0 94.19 −301.6 2.48 1.06

2.722 −2144 4.949 −4448 −237.6 546.0 1100

3.63 2.07 ethanol + water A1 B1 A2 B2 J0 J1 J2

2.19 1.71 J0 J1 J2

Apelblat− Jouyban−Acree

value

3.29 6.66

3.51 2.07 J0 J1 J2

RAD × 102 RMSD × 104

van’t Hoff− Jouyban−Acree value

5.223 −2843 4.949 −4448 370.7 505.5 −776.5

1.93 0.83 isopropanol + water A1 B1 A2 B2 J0 J1 J2

3.28 1.83

5.165 −2956 4.949 −4448 693.2 95.59 −300.9

2.65 1.16

Here, xL1,3 refers to the local mole fraction of solvent (1) in the environment nearby terephthalaldehydic acid (3), and x1 denotes the bulk mole fraction composition of solvent (1) in the initial mixtures. The δx1,3 parameter signifies the deficiency or excess of solvent in solvent mixtures in the local region. When terephthalaldehydic acid is preferentially solvated by ethanol, NMP, methanol, or isopropanol (1), δx1,3 is greater than 0, whereas when δx1,3 is less than 0, the terephthalaldehydic acid is said to be preferentially solvated by water (2). However, when |δx1,3| is less than 0.01, the preferential solvation procedure may

be negligible; nevertheless, if xL1,3 is approximately equal to 1, then complete solvation of terephthalaldehydic acid is performed by the ethanol, NMP, methanol, or isopropanol (1). The parameter δx1,3 in solvent (1) and water (2) mixtures can be obtainable by using the inverse Kirkwood−Buff integrals (IKBI) for the individual solvent components:27−31 δx1,3 = G

x1x 2(G1,3 − G2,3) x1G1,3 + x 2G2,3 + Vcor



Article

Table 7. Gibbs Energy of Transfer (kJ·mol−1) of Terephthalaldehydic Acid (3) from Neat Water (2) to Methanol (1) + Water (2), Ethanol (1) + Water (2), Isopropanol (1) + Water (2), and NMP (1) + Water (2) Solvent Mixtures at 298.15 K methanol (1) + water (2) x1a 0 0.05882 0.1233 0.1942 0.2727 0.3600 0.4576 0.5675 0.6923 0.8350 1

ethanol (1) + water (2)

ΔtrG

x1a

0 −1.472 −2.462 −3.498 −5.068 −6.168 −7.935 −9.85 −11.67 −12.80 −13.66

0 0.04135 0.08908 0.1436 0.2068 0.2812 0.3698 0.4772 0.6101 0.7788 1

o

isopropanol (1) + water (2)

ΔtrG

x1a

ΔtrG

0 −0.976 −2.634 −4.178 −6.044 −7.869 −9.282 −10.60 −11.70 −12.81 −14.03

0 0.03229 0.06983 0.1140 0.1668 0.2309 0.3105 0.4120 0.5457 0.7299 1

0 −1.625 −3.361 −4.847 −6.469 −7.933 −9.238 −10.24 −11.17 −12.17 −12.96

o

o

NMP (1) + water (2) x1a

ΔtrGo

0 0.01980 0.04347 0.07228 0.1081 0.1538 0.2143 0.2978 0.4210 0.6206 1

0 −3.133 −5.479 −7.217 −9.127 −10.90 −12.32 −13.94 −15.57 −17.48 −19.13

a a x1 represents the molar fraction of methanol (ethanol, isopropanol, or NMP) in mixed solvents of methanol (ethanol, isopropanol, or NMP) (w) and water (1 − w) free of terephthalaldehydic acid.

with G1,3 = RTκT − V3 +

x 2 V2D Q

(15)

G2,3 = RTκT − V3 +

x1V1D Q

(16)

The standard molar Gibbs energy of transfer of terephthalaldehydic acid from pure water (2) to NMP (1) and water (1), ethanol (1) and water (1), methanol (1) and water (1), and isopropanol (1) and water (1) mixtures at 298.15 K is calculated from the solubility data by using eq 22 and presented in Table 7. These values are shown graphically in Figure 6. jij x3,2 zyz 0 j zz Δtr G3,2 → 1 + 2 = RT lnj jx z k 3,1 + 2 {

L L Vcor = 2522.5[r3 + 0.1363(x1,3 V1̅ + x 2,3 V2)1/3 − 0.085]3

(17)

(22)

In eqs 14−17, V̅ 1 and V̅ 2 refer to the partial molar volumes of solvents in the solvent mixtures; in the same way, V̅ 3 denotes the partial molar volume of terephthalaldehydic acid in the solutions. The function D expressed as eq 18 refers to the derivative of standard molar Gibbs energies of transfer of terephthalaldehydic acid from pure water (2) to the solvent mixtures of solvent (1) and water (2) with respect to the solvent composition. The function Q described as eq 19 comprises the second derivative of the excess molar Gibbs energy of mixing of two solvents (GExc 1+2) with respect to the water fraction in the solvent mixtures. Vcor stands for the correlation volume, and r3 denotes the molecular radius of terephthalaldehydic acid evaluated by using eq 20 with NAv as Avogadro’s number. o ij ∂Δtr G(3,2 → 1 + 2) y zz zz D = jjj j z ∂ x 1 k {T,P ÅÄÅ 2 Exc ÑÉÑ Å ∂ G1 + 2 ÑÑ ÑÑ Q = RT + x1x 2ÅÅÅÅ ÅÅ ∂x 22 ÑÑÑ ÅÇ ÑÖT,p

r3 =

3

3 × 1021V3 4πNAV

Figure 6. Gibbs energy of transfer (kJ·mol−1) of terephthalaldehydic acid (3) from neat water (2) to methanol (1) and water (2), NMP (1) and water (2), ethanol (1) and water (2), and isopropanol (1) and water (2) mixtures at 298.15 K. ■, NMP (1) and water (2); ●, methanol (1) and water (2); ▲, ethanol (1) and water; ▼, isopropanol (1) and water (2).

(18)

(19)

The ΔtrG03,2→1+2 values are correlated with eq 23 for the four solvent (1) and water (2) mixtures.

(20)

0 −x1/ t1 Δtr G3,2 + A 2 e−x1/ t2 → 1 + 2 = A 0 + A1 e

κT refers to the isothermal compressibility of solvent mixtures of solvent (1) and water (2; in GPa−1). Because of the slight contribution of RTκT to the inverse Kirkwood−Buff integral, the κT dependence on solvent composition will be obtained approximated by considering additive behavior from individual isothermal compressibility of pure components on the basis of eq 21.27,28,30,31 ° ° κT = x1κT,1 + x 2κT,2

(23)

Here, A0, A1, A2, t1, and t2 are equation parameters. The regressed equation coefficients are listed in Table 8. Therefore, the D values are obtainable from the first derivative of eq 23 solved according to the solvent composition changing by 0.05 in mole fraction of solvent (1) and presented in Tables 9−12. Due to no partial molar volumes of terephthalaldehydic acid (3) in these mixtures available in the previous publications, it is regarded as similar to that for the pure compound. Here, the

(21) H



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Table 8. Coefficients of eq 23 (kJ·mol−1) Applied to Gibbs Energy of Transfer of Terephthalaldehydic Acid ((3) from Neat Water (2) to Methanol (1) + Water (2), Ethanol (1) + Water (2), Isopropanol (1) + Water (2) and NMP (1) + Water (2) Solvent Mixtures at 298.15 K coefficient

NMP (1) + water (2)

methanol (1) + water (2)

ethanol (1) + water (2)

isopropanol (1) + water (2)

A0 A1 t1 A2 t2

−20.00 13.78 0.3646 6.144 0.04546

−23.35 11.71 1.072 11.71 1.072

−15.10 7.717 0.3909 7.717 0.3909

−40905 10.55 0.1944 40895 16256

Table 10. Some Properties Associated with Preferential Solvation of Terephthalaldehydic Acid (3) in Methanol (1) + Water (2) Mixtures at 298.15 K

Table 9. Some Properties Associated with Preferential Solvation of Terephthalaldehydic Acid (3) in NMP (1) + Water (2) Mixtures at 298.15 K x1a

D kJ·mol−1

G1,3 cm3·mol−1

G2,3 cm3·mol−1

Vcor cm3·mol−1

100 δx1,3

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

−172.9 −77.93 −43.69 −30.02 −23.49 −19.58 −16.78 −14.53 −12.63 −11.00 −9.590 −8.360 −7.288 −6.354 −5.540 −4.830 −4.211 −3.672 −3.201 −2.791 −2.433

−1378.4 −705.4 −427.7 −306.7 −245.6 −209.4 −185.5 −168.7 −156.4 −147.1 −139.8 −134.0 −129.3 −125.3 −122.0 −119.3 −117.1 −115.4 −114.1 −113.1 −112.4

−112.5 −268.6 −290.1 −288.9 −286.4 −284.1 −281.7 −279.1 −276.6 −274.1 −271.5 −268.3 −264.0 −258.2 −250.4 −241.1 −231.0 −221.0 −212.5 −207.1 −207.0

627.7 603.9 724.4 823.3 905.6 979.3 1047 1112 1173 1233 1290 1346 1401 1454 1507 1558 1609 1660 1711 1762 1813

0 −6.620 −2.945 −0.428 1.041 1.964 2.542 2.883 3.053 3.096 3.035 2.886 2.656 2.357 2.004 1.623 1.240 0.881 0.558 0.271 0

x1a

D kJ·mol−1

G1,3 cm3·mol−1

G2,3 cm3·mol−1

Vcor cm3·mol−1

100 δx1,3

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

−21.85 −20.85 −19.90 −18.99 −18.13 −17.30 −16.51 −15.76 −15.04 −14.36 −13.70 −13.08 −12.48 −11.92 −11.37 −10.85 −10.36 −9.888 −9.438 −9.008 −8.597

−272.1 −255.3 −243.3 −234.2 −226.8 −220.2 −213.7 −206.7 −198.7 −189.7 −179.7 −169.1 −158.5 −148.6 −139.7 −132.1 −125.8 −120.7 −116.6 −113.3 −110.6

−112.5 −127.8 −142.4 −157.4 −173.1 −189.8 −207.3 −225.2 −242.6 −258.1 −270.5 −278.7 −282.3 −281.8 −278.2 −272.5 −266.2 −260.1 −255.2 −252.1 −251.9

626.9 640.8 656.9 675.0 694.6 715.7 738.0 761.2 784.9 808.5 831.6 853.6 874.5 894.2 913.2 931.5 949.6 967.6 985.6 1004 1022

0 −1.196 −1.800 −1.936 −1.683 −1.101 −0.252 0.779 1.879 2.912 3.741 4.269 4.458 4.337 3.974 3.446 2.823 2.152 1.458 0.747 0

a

x1 is the mole fraction of methanol (1) in the methanol (1) + water (2) mixtures free of terephthalaldehydic acid (3).

Table 11. Some Properties Associated with Preferential Solvation of Terephthalaldehydic Acid (3) in Ethanol (1) + Water (2) Mixtures at 298.15 K

a

x1 is the mole fraction of NMP (1) in the NMP (1) + water (2) mixtures free of terephthalaldehydic acid (3).

molar volume Vs = 113.6 cm3·mol−1 is used according to the SciFinder database (https://scifinder.cas.org/scifinder/view/ scifinder/scifinderExplore.jsf). So the solute radius value (r3) is obtained by using eq 20 as 0.356 nm. Moreover, the values of RTκT, Q, and the partial molar volumes of both solvents in the ethanol (1) and water (2), NMP (1) and water (2), methanol (1) and water (2), and isopropanol (1) and water (2) mixtures at 298.15 K can be found in refs 27, 30, and 31. Consequently, the values of G1,3 and G2,3 in the four binary solvent mixtures can be obtainable and are presented in Tables 9−12. It shows that the values of G1,3 and G2,3 are negative in all cases, demostrating that terephthalaldehydic acid exhibits affinity for the selected solvent mixtures. The iterated values of Vcor and δx1,3 are also presented in Tables 9−12 for terephthalaldehydic acid dissolved in NMP (1) and water (2), ethanol (1) and water (2), methanol (1) and water (2), and isopropanol (1) and water (2) solvent mixtures, respectively. The plots of δx1,3 versus solvent 1 (NMP, ethanol, methanol, and isopropanol) compositions are given in Figure 7. It may be observed that the dependence of δx1,3 values upon the

x1a

D kJ·mol−1

G1,3 cm3·mol−1

G2,3 cm3·mol−1

Vcor cm3·mol−1

100 δx1,3

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

−39.49 −34.75 −30.57 −26.90 −23.67 −20.83 −18.33 −16.13 −14.19 −12.49 −10.99 −9.668 −8.507 −7.486 −6.587 −5.796 −5.100 −4.488 −3.949 −3.475 −3.057

−400.1 −380.6 −355.4 −327.2 −298.8 −272.2 −248.4 −228.0 −210.8 −196.4 −184.3 −174.0 −164.7 −155.8 −146.6 −136.9 −127.6 −120.0 −115.0 −112.2 −110.8

−112.5 −154.7 −194.1 −228.3 −256.6 −279.4 −297.8 −313.6 −328.1 −342.8 −358.7 −376.2 −394.6 −410.5 −417.3 −405.6 −370.3 −317.8 −262.9 −216.8 −183.0

625.9 645.2 673.6 710.8 753.6 798.2 842.0 884.2 924.6 963.3 1001 1037 1071 1104 1134 1160 1184 1208 1233 1261 1291

0 −2.239 −3.133 −2.697 −1.382 0.260 1.857 3.242 4.376 5.279 5.978 6.485 6.770 6.744 6.273 5.269 3.853 2.384 1.207 0.435 0

a

x1 is the mole fraction of ethanol (1) in the ethanol (1) + water (2) mixtures free of terephthalaldehydic acid (3).

solvent (1) proportion in the mixed solvents is nonlinear. On the basis of Figure 7, the addition of solvent (NMP, ethanol, methanol, and isopropanol) makes negative the δx1,3 values of terephthalaldehydic acid (3) from pure water up to an x1 = 0.16 I



Article

mixtures, where terephthalaldehydic acid is preferentially solvated by water, terephthalaldehydic acid can act mainly as a Lewis base in front of water because the Kamlet−Taft hydrogen bond donor parameters are α = 1.17 for water, 0.99 for methanol, 0.86 for ethanol, 0.76 for isopropanol, and 0 for NMP, respectively.32 In the NMP (1) and water (2) mixtures with compositions 0.16 < x1 < 1, methanol (1) and water (2) mixtures with compositions 0.32 < x1 < 1, and ethanol (1) and water (2) and isopropanol (1) and water (2) mixtures with compositions 0.25 < x1 < 1, the local mole fractions of NMP (ethanol, methanol, and isopropanol) are higher than that of the mixtures, and consequently the δx1,3 values are positive, which indicates preferential solvation of terephthalaldehydic acid by the NMP (ethanol, methanol, and isopropanol). The NMP (ethanol, methanol, and isopropanol) action to increase the solute solubility is perhaps related to breaking of the ordered structure of water around the nonpolar moieties of terephthalaldehydic acid, which increases the solvation, having maximum values in x1 = 0.45 with δx1,3 = 3.096 × 10−2 for NMP (1) and water (2) mixture, x1 = 0.60 with δx1,3 = 4.458 × 10−2 for methanol (1) and water (2) mixture, x1 = 0.60 with δx1,3 = 6.770 × 10−2 for ethanol (1) and water (2) mixture, and x1 = 0.60 with δx1,3 = 14.65 × 10−2 for isopropanol (1) and water (2) mixture. Terephthalaldehydic acid acts as a Lewis acid with NMP, ethanol, methanol, or isopropanol molecules, because these solvents are more basic than water, as described by the Kamlet−Taft hydrogen bond acceptor parameters, i.e., β = 0.77 for NMP, β = 0.99 for methanol, 0.75 for ethanol, β = 0.84 for isopropanol, and β = 0.47 for water.32 It can also be seen that in the intermediate and solvent 1-rich compositions, the preferential solvation magnitudes of terephthalaldehydic acid by solvent 1 are highest in isopropanol mixtures, followed by ethanol mixtures, and finally by NMP mixtures in different solvent 1 proportions.

Table 12. Some Properties Associated to Preferential Solvation of Terephthalaldehydic Acid (3) in Isopropanol (1) + Water (2) Mixtures at 298.15 K x1a

D kJ·mol−1

G1,3 cm3·mol−1

G2,3 cm3·mol−1

Vcor cm3·mol−1

100 δx1,3

0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00

−56.76 −44.46 −34.95 −27.60 −21.91 −17.51 −14.11 −11.48 −9.448 −7.876 −6.660 −5.720 −4.994 −4.432 −3.997 −3.661 −3.401 −3.200 −3.045 −2.925 −2.832

−526.0 −429.7 −362.7 −315.2 −281.2 −256.9 −240.0 −228.9 −222.8 −220.8 −221.7 −222.2 −214.4 −191.8 −162.0 −138.6 −124.8 −117.4 −113.6 −111.5 −110.3

−112.5 −162.5 −196.5 −221.8 −242.9 −263.4 −286.4 −315.3 −354.5 −409.7 −486.3 −581.1 −659.7 −654.4 −553.3 −428.8 −331.5 −266.3 −224.0 −196.1 −177.2

625.9 641.8 672.7 712.2 754.8 798.0 841.1 884.5 928.9 975.6 1026 1077 1122 1146 1154 1163 1180 1204 1231 1260 1291

0 −2.724 −3.254 −2.499 −1.213 0.229 1.714 3.279 5.042 7.182 9.848 12.81 14.65 13.28 9.393 5.713 3.261 1.785 0.899 0.351 0

a

x1 is the mole fraction of isopropanol (1) in the isopropanol (1) + water (2) mixtures free of terephthalaldehydic acid (3).

■

CONCLUSION The liquid−solid equilibrium solubility of terephthalaldehydic acid dissolved in mixed solvents of ethanol, methanol, isopropanol, and NMP and water was achieved experimentally through the isothermal dissolution equilibrium method at temperatures from 283.15 to 323.15 K under about 101.1 kPa. For all solvent mixures, the mole fraction solubility of terephthalaldehydic acid increased with an increase in temperature and mass fraction of ethanol (methanol, isopropanol, and NMP) for the ethanol (methanol, isopropanol, and NMP) and water mixtures, and the largest mole fraction solubility value of terephthalaldehydic acid was observed in neat ethanol (methanol, isopropanol, and NMP). The change of terephthalaldehydic acid solubility with ethanol (methanol, isopropanol, and NMP) composition and temperature was correlated through Jouyban−Acree, Van’t Hoff−Jouyban−Acree, and Apelblat−Jouyban−Acree models obtaining RAD and RMSD values no larger than 3.63 × 10−2 and 6.66 × 10−4, respectively. The Jouyban−Acree model was more suitable for describing the terephthalaldehydic acid solubility in the selected solvent mixtures. The local mole fraction of NMP (ethanol, methanol, or isopropanol) and water nearby terephthalaldehydic acid was derived through the IKBI technique applied to the solubility data determined at 298.15 K. Terephthalaldehydic acid was preferentially solvated by water in water-rich compositions for the selected mixtures, while in the other regions, terephthalaldehydic acid was preferentially solvated by NMP (ethanol, methanol, or isopropanol).

Figure 7. δx1,3 values of terephthalaldehydic acid (3) in methanol (1) and water (2), ethanol (1) and water (2), isopropanol (1) and water (2), and NMP (1) and water (2) mixtures at 298.15 K. ■, NMP (1) and water (2); ●, methanol (1) and water (2); ▲, ethanol (1) and water; ▼, isopropanol (1) and water (2).

mole fraction of NMP, x1 = 0.32 mole fraction of methanol, and x1 = 0.25 mole fraction of ethanol and isopropanol. Maximum negative values are acquired with the solvent (1) composition x1 = 0.05 with δx1,3 = −6.620 × 10−2 for the NMP (1) + water (2), x1 = 0.15 with δx1,3 = −1.936 × 10−2 for the methanol (1) and water (2), x1 = 0.10 with δx1,3 = −3.133 × 10−2 for the ethanol (1) and water (2) and δx1,3 = −3.254 × 10−2 for isopropanol (1) and water (2) mixtures, respectively. Perhaps the structuring of water molecules nearby the nonpolar aromatic group of terephthalaldehydic acid contributes to lowering of the net δx1,3 values to negative in the four mixtures. In water-rich solvent J



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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.8b01262. Mole fraction solubility (x) of terephthalaldehydic acid in water (Table S1) and mole fraction solubility (x) of terephthalaldehydic acid in NMP (Table S2) (PDF)

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AUTHOR INFORMATION

Corresponding Author

*Tel.: + 86 514 87975244. E-mail: [email protected]. ORCID

Hongkun Zhao: 0000-0001-5972-8352 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We express our thanks to the academic innovation fund for university students in Yangzhou University (Project number: X20180220) and “Dawn Project” for innovation and entrepreneurship (Project number: CX2018065) for their financial assistances in this paper.

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REFERENCES

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