Measurement and Correlation of the Dissolution Equilibria of o

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

pubs.acs.org/jced

Measurement and Correlation of the Dissolution Equilibria of o‑Iodoaniline and p‑Iodoaniline in Pure Solvents Kui Xu,† Jing Zhu,† and Tianxiang Li*,†,‡ †

School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou 550025, China National Key Laboratory of Efficient Utilization of Low Grade Phosphate Rocks and Its Associated Resources, Fuquan, Guizhou 550500, China

‡

ABSTRACT: By the laser technique, data on the solubilities of o-iodoaniline and p-iodoaniline in 12 pure solvents (water, methanol, ethylene glycol, ethyl acetate, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, ethanol, isopropanol, and benzene) from 273 to 333 K were measured. The data were correlated with NRTL model, the Apelblat equation, the λh equation, and the van’t Hoff equation. The results indicate that the Apelblat equation gave the best fitting results.

1. INTRODUCTION Iodoanilines are halogenated aniline compounds that are widely used in many fields benefiting from the low toxicity and high activity of iodine. o-Iodoaniline is an important intermediate for the synthesis of many drugs, such as quinolines,1 indoles,2 coumarones,2 benzothiazoles,3 benzimidazoles,4 oximes,5 etc. pIodoaniline is an organic synthesis intermediate for dyes,6 medicines, and pesticides, such as the non-cytotoxic biological radiopacity material with p-iodoaniline as the end-capper,7 cyclodextrin,8 and radiolabeled insulin.9 Also, m-iodoaniline can be used to develop conductive materials.10 Usually miodoaniline is prepared by reduction of m-iodonitrobenzene with high purity.11 The synthesis processes of p-iodoaniline are well-developed: it can be either synthesized directly by using aniline, iodine, sodium bicarbonate, and water at low temperature12 or produced by reduction of p-iodonitrobenzene,13 both with ideal yield. As for o-iodoaniline, the synthesis processes (reaction between aniline and iodine or iodide,14,15 iodination of o-nitroaniline, reduction of o-iodonitrobenzene,16,17 rearrangement of p-iodoaniline into o-iodoaniline,18 etc.) are often accompanied by the formation of p-iodoaniline, and isomer separation is always needed to obtain the pure product. In order to obtain high-purity o-iodoaniline by extraction and crystallization, accurate and systematic measurements of the solubilities of o-iodoaniline and p-iodoaniline in different solvents are necessary. On the basis of these data, crystal © XXXX American Chemical Society

products with lower impurity incorporation, larger particle sizes, and narrower size distributions can be obtained. The laser technique can be used as a quantitative analysis tool for the dissolution equilibria. When the solute crystallizes from the solution, the turbidity of the system increases, resulting in a reduction in the amount of laser light that can be absorbed by the solution, while the amount of transmitted laser decreases.19 Similarly, when the solute starts dissolution, the amount of transmitted laser light increases. In this work, the solubilities of o-iodoaniline and piodoaniline in water, methanol, ethylene glycol, ethyl acetate, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, ethanol, isopropanol, and benzene from 273 to 333 K were measured using the laser technique. The thermodynamic phase equilibrium data were analyzed for the same solute in different solvents as well as different solutes in the same solvent. Besides, to extend the application of the data, the nonrandom two-liquid (NRTL) model, the Apelblat equation, the λh equation, and the van’t Hoff equation were employed to correlate the solubilities. Received: September 20, 2017 Accepted: December 1, 2017

A

DOI: 10.1021/acs.jced.7b00840 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Description of Instruments Used in This Work device

model

manufacturer

electronic balance water bath with magnetic stirring cryogenic thermostatic bath mercury thermometer laser receiver He−Ne laser jacketed crystallizer

HX-T(100Z) 85-2A DC-4006 0−50 °C (±0.05 °C) JG2-0503011 JDW-3 200 mL

Zhejiang Cixi Tianyi Weighing Apparatus Factory, China Changzhou Putian Instrument Manufacturing Co., Ltd., China Shanghai Equitable Instrument and Meter Factory, China Hebei Jixian Yaohua Glass Instrument Factory, China Department of Physics, Peking University, China Department of Physics, Peking University, China self-made

Table 2. Description of Organic Solvents Used in This Worka CAS no.

massfraction purity

ethylene glycol

107-21-1

>0.990

methanol

67-56-1

>0.995

ethyl acetate

141-78-6

>0.995

hexane

110-54-3

>0.970

cyclohexane

110-82-7

>0.995

dichloromethane

75-09-2

>0.995

trichloromethane

8013-54-5

>0.995

tetrachloromethane

56-23-5

>0.995

ethanol

64-17-5

>0.997

isopropanol

67-63-0

>0.997

benzene

71-43-2

>0.995

p-iodoaniline

540-37-4

>0.998

o-iodoaniline

615-43-0

>0.998

potassium chloride

7447-40-7

>0.995b

materials

source Chongqing Jiangchuan Chemical Co., Ltd., China Tianjin Fuyu Fine Chemical Co., Ltd., China Tianjin Fuyu Fine Chemical Co., Ltd., China Tianjin Fuyu Fine Chemical Co., Ltd., China Chongqing East Sichuan Chemical (Group) Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Chengdu Jinshan Chemical Reagent Co., Ltd., China Shandong Weifang Fine Chemicals Co., Ltd., China Shandong Weifang Fine Chemicals Co., Ltd., China Tianjin Youpu Chemical Reagent Co., Ltd., China

a The solvents and solutes were detected by gas chromatography. bThe sample purity was stated by the supplier.

Figure 1. PXRD patterns of raw and excess iodoanilines from ethyl alcohol at T = 293.15 K.

2. EXPERIMENTAL SECTION 2.1. Experimental Instruments and Materials. The instruments and organic solvents used in this paper are listed in Table 1 and Table 2, respectively. The melting points of iodoaniline products (331.95−332.75 K for p-iodoaniline and 325.15−326.25 K for o-iodoaniline) were in accordance with literature values.20 The melting point data were collected on a micro melting point apparatus (type X-5, Gongyi Yuhua Instrument Co., Ltd., China) using capillary tubes and a heating rate of 0.2 K·min−1. Deionized water was prepared using Molatan 1820S (Chongqing Mole Water Treatment Co., Ltd., China). 2.2. X-ray Powder Diffraction Analysis. The polymorphs of iodoaniline were analyzed by X-ray powder diffraction (XRPD). The raw iodoaniline and excess iodoaniline in the 12 pure solvents were tested. The data were collected on an X’Pert powder diffractometer (PANalytical B.V., The Netherlands)

Table 3. KCl−H2O Experimental and Literature Solubility Data (p = 0.1 MPa)a T/K

xlit

T/K

xexp

273.15 283.15 293.15 303.15 313.15 323.15

0.0634 0.0706 0.0778 0.0846 0.0912 0.0968

278.15 288.35 292.95 303.15 313.15 323.15

0.0667 0.0736 0.0775 0.0836 0.0904 0.0946

a

xexp and xlit are the experimental and literature solubilities, respectively. The standard uncertainties u are u(T) = 0.1 K and u(p) ≈ 1 kPa. The relative standard uncertainty of the solubility measurements is ur(x) = 0.06.

using Cu Kα radiation (λ = 0.15406 nm) in the 2θ range of 5− 60° at a scan rate of 8 deg·min−1. B



Article

Table 4. Experimental (xexp) and Calculated (xcal) Mole-Fraction Solubilities of p-Iodoaniline (p = 0.1 MPa) T/K

102·xexp

283.95 287.35 290.25 295.45 298.45 304.75 309.05 314.05 323.05

0.00932 0.0105 0.0121 0.0145 0.0163 0.0204 0.0243 0.0281 0.0316

277.65 282.55 287.70 292.05 297.95 303.35 305.15 311.55 319.25

9.17 10.9 12.8 15.7 19.4 26.5 29.0 39.8 48.4

280.25 284.75 288.85 293.75 298.55 303.55 308.95 313.75 318.55 323.15

6.31 6.89 7.61 8.61 9.91 11.7 14.2 18.2 24.1 35.7

275.85 283.65 289.05 293.55 296.55 300.45 305.35 310.45 313.55 316.15

32.8 36.8 39.9 43.5 46.7 49.0 53.7 59.3 63.5 66.7

281.65 283.65 288.35 294.5 298.55 303.00 308.25 313.05 315.85 320.35

0.380 0.421 0.501 0.707 0.800 1.05 1.32 1.77 2.11 2.51

283.85 288.75 293.15 298.45 304.15 309.65

0.681 0.819 0.952 1.28 1.71 2.37

102·xNRTL cal Deionized Water 0.00932 0.0105 0.0115 0.0136 0.0149 0.0181 0.0205 0.0236 0.0302 Methanol 9.17 11.8 15.2 18.7 24.5 31.1 33.6 43.9 59.9 Ethylene Glycol 3.71 4.83 6.10 7.99 10.3 13.4 17.5 22.1 27.7 34.1 Ethyl Acetate 31.0 35.5 38.8 41.7 43.7 46.4 49.9 53.7 56.1 58.1 Hexane 0.376 0.424 0.560 0.795 0.993 1.259 1.65 2.10 2.41 2.99 Cyclohexane 0.523 0.787 1.12 1.69 2.61 3.88

a

102·xApel cal

102·xλh cal

T/K

102·xexp

102·xNRTL cal

102·xApel cal

102·xλh cal

0.00875 0.0104 0.0120 0.0150 0.0169 0.0210 0.0238 0.0270 0.0321

0.0128 0.0133 0.0137 0.0147 0.0154 0.0175 0.0194 0.0228 0.0362

282.45 285.75 289.75 293.75 298.55 305.55 312.35

20.9 23.6 27.1 30.8 35.6 42.2 54.9

Dichloromethane 20.4 22.7 25.7 29.2 33.7 41.2 49.8

21.4 23.7 26.7 30.2 35.1 43.7 54.3

21.0 23.5 26.8 30.5 35.5 44.0 53.7

66.9 62.9 55.1 46.0 39.6 35. 30.7 23.4 20.7 19.7

67.0 62.9 55.1 45.9 39.5 35.1 30.7 23.4 20.7 19.7

10.5 17.1 24.1 35.5 46.8 64.8

8.51 15.7 24.1 37.0 48.6 63.5

7.97 10.3 13.3 16.3 21.3 26.8 28.9 37.2 49.5

8.63 10.8 13.5 16.3 20.9 26.2 28.3 36.8 50.6

319.95 317.75 313.25 307.45 302.85 299.35 295.55 288.15 285.05 283.75

66.8 62.6 55.7 46.1 39.3 35.2 30.4 23.2 20.8 19.8

6.58 6.77 7.20 8.05 9.36 11.4 14.7 19.0 25.4 34.5

5.08 5.98 6.96 8.37 10.1 12.4 15.6 19.6 25.2 33.2

303.55 308.15 311.65 315.75 318.85 322.65

10.1 15.2 21.1 39.9 48.5 62.9

Trichloromethane 66.8 62.5 54.4 45.3 38.9 34.6 30.3 23.2 20.7 19.7 Tetrachloromethane 9.8 14.5 19.4 27.0 34.5 46.2

32.7 36.9 40.3 43.5 45.9 49.2 53.9 59.5 63.3 66.7

32.3 36.9 40.4 43.7 46.1 49.4 54.0 59.5 63.1 66.4

320.35 313.15 309.05 304.35 298.55 293.35 287.65

64.1 43.7 30.8 22.9 17.3 13.9 10.9

Ethanol 64.0 42.9 33.9 25.7 18.0 12.9 8.88

63.9 42.2 33.1 25.0 17.5 12.6 8.76

61.1 43.2 34.3 25.7 17.3 11.8 7.47

0.358 0.396 0.502 0.687 0.844 1.06 1.38 1.76 2.03 2.55

0.439 0.471 0.557 0.705 0.830 1.00 1.29 1.66 1.96 2.68

318.05 313.25 308.55 303.85 300.05 295.05 291.45

53.6 36.6 23.9 16.9 13.1 10.3 8.81

Isopropanol 53.5 38.3 27.3 19.3 14.4 9.73 7.27

52.8 36.8 25.7 17.8 13.2 8.87 6.63

50.9 37.7 26.8 18.3 13.1 8.14 5.68

0.406 0.584 0.807 1.18 1.76 2.57

0.635 0.805 1.001 1.31 1.77 2.43

320.65 313.25 307.95 302.65 297.95 292.15

73.0 57.5 45.8 36.5 30.4 23.7

Benzene 73.0 54.8 44.3 35.5 29.0 22.4

74.3 55.7 45.2 36.6 30.2 23.8

71.9 57.0 46.9 37.7 30.4 22.7

C



Article

Table 4. continued T/K 314.05 318.85 323.35

102·xexp 3.30 4.67 6.60

102·xNRTL cal Cyclohexane 5.29 7.35 9.91

102·xApel cal

102·xλh cal

T/K

102·xexp

102·xNRTL cal

102·xApel cal

102·xλh cal

3.47 4.77 6.41

3.21 4.53 6.69

288.15

18.8

Benzene 18.6

20.2

18.3

Apel λh xexp, xNRTL cal , xcal , and xcal represent the experimental solubility and the solubilities calculated data using the NRTL, Apelblat, and λh models, respectively. The standard uncertainties u are u(T) = 0.1 K and u(p) ≈ 1 kPa. The relative standard uncertainty of the solubility measurements is ur(x) = 0.06. a

methane, trichloromethane, benzene, and tetrachloromethane, the solubility of o-iodoaniline is higher. In ethyl acetate, however, the solubilities of o-iodoaniline and p-iodoaniline are similar. At a given temperature, the order of solubility for oiodoaniline is water < hexane < cyclohexane ≈ ethylene glycol < isopropanol < ethanol ≈ methanol < tetrachloromethane < benzene < trichloromethane ≈ dichloromethane < ethyl acetate, and the order for p-iodoaniline is water < hexane < cyclohexane < ethylene glycol < tetrachloromethane < isopropanol < ethanol < methanol < benzene < trichloromethane < dichloromethane < ethyl acetate. Overall, the polarity of the solvent, the formation of hydrogen bonds between solute and solvent molecules, and the steric structures of the solute and solvent molecules all can influence the solubility of iodoaniline. 3.2. Correlation of Iodoaniline Solubility Data. Because of the different interactions between solute and solvent molecules, the ideal solution model cannot be used directly to correlate the solubility data. This section describes the four common dissolution equilibrium models that were employed to fit the solubility data. NRTL Model. According to basic thermodynamic principles, the universal solubility equation can be described as follows:22

The XRPD patterns of iodoaniline show that all of the samples used in this experiment have good stability. Figure 1 indicates that the raw iodoaniline and excess iodoaniline (from ethyl alcohol at T = 293.15 K as an example) crystal forms were the same during this experiment. 2.3.1. Solubility Measurements. The solubility data for oiodoaniline and p-iodoaniline from 273 to 333 K were measured using the laser method. A slight excess of iodoaniline was added to the jacketed crystallizer with about 30 mL of solvent in it, and the solution was stirred with a magnetic stirrer at a speed of 300 revolutions·min−1 (lower speeds allowed the solute to sink to the bottom, and higher speeds caused vortexing and laser refraction). Then pure solvent was gradually added into the crystallizer with a buret at a rate of 0.5 mL over 10 min to ensure that the temperature was stable. During this process, the laser beam was sent through the crystallizer, and the intensity of the transmitted laser light was measured. When the dissolution was complete, the laser intensity value should reach the maximum. The light intensity was plotted against the amount of solvent, and the solubility of iodoaniline was calculated from the maximum light intensity concentration. Experiments were done in triplicate to minimize the measuring error, and the average value was taken as the solubility for each temperature point. The temperature was controlled using a cryogenic thermostatic bath with a precision of ±0.05 K. The mole-fraction solubility of iodoaniline (x) was calculated using eq 1: m1/M1 x= m1/M1 + m2 /M 2

ln(xγ ) =

⎛ Ttp ⎞⎤ ΔHtp ⎛ Ttp ⎞ ΔCp ⎡ Ttp ⎢ − 1 − ln⎜ ⎟⎥ ⎜1 − ⎟+ RTtp ⎝ T ⎠ R ⎣T ⎝ T ⎠⎦ −

(1)

ΔV (P − Ptp) RT

(2)

where x is the mole-fraction solubility, γ is the activity coefficient of the solute, R is the gas constant, the subscript “tp” represents the triple point, ΔCp represents the molar heat capacity dierence between the solid and liquid state of the solute at the melting point, T represents the absolute temperature, V represents volume and P represents pressure. Under normal pressure, the pressure and ΔCp correction terms can be ignored, and eq 2 can be simplified to

where m1 and m2 represent the masses and M1 and M2 the molar masses of the solute and solvent, respectively. 2.3.2. Method Validation. The method was validated on the KCl−H2O binary system, and the experimental data were in accordance with the literature data (Table 3).21 The average relative deviation of the experimental data was less than 1.07%, indicating that the solubility data measured by the experimental apparatus are reliable.

ln x1 =

3. RESULTS AND DISCUSSION 3.1. Solubilities of Iodoaniline. The experimental molefraction solubilities xexp of p-iodoaniline and o-iodoaniline are listed in Table 4 and Table 5, respectively, and depicted in Figure 2 and Figure 3, respectively. As can be observed in Figure 2 and Figure 3, the solubility of iodoaniline increases with increasing temperature for all 24 systems, and the solubilities in methanol, isopropanol, ethanol, ethylene glycol, ethyl acetate, benzene, dichloromethane, and trichloromethane are higher than those in water, hexane, and cyclohexane for both solutes. In water, methanol, ethanol, isopropanol, and ethylene glycol, the solubility of p-iodoaniline is higher than that of o-iodoaniline, while in hexane, cyclohexane, dichloro-

ΔHtp ⎛ Ttp ⎞ ⎜1 − ⎟ − ln γ1 RTtp ⎝ T ⎠

(3)

The well-established NRTL model solute activity coefficient:

22

was used to derive the

⎡ τ G 2 ⎤ τ12G12 21 21 ⎥ ln γ1 = x 2 2⎢ + 2 2 (x 2 + x1G12) ⎦ ⎣ (x1 + x 2G21)

(4)

where x1 and x2 = 1 − x1 are the mole fractions of the solute and solvent, respectively, and ln G12 = −α12τ12 ln G21 = −α21τ21 D



Article

Table 5. Experimental (xexp) and Calculated (xcal) Mole-Fraction Solubilities of o-Iodoaniline (p = 0.1 MPa) T/K

102·xexp

308.15 302.35 299.35 296.55 293.05 290.65 287.05 284.55 279.35

0.0146 0.0135 0.0126 0.0115 0.0103 0.00921 0.00815 0.00737 0.00622

313.05 310.15 306.25 299.35 296.25 290.75 285.25 281.15

45.1 39.9 24.7 14.7 12.5 9.60 7.70 6.47

311.35 307.95 303.15 299.25 293.15 289.55 285.45 280.55

8.72 7.51 5.85 5.09 4.13 3.64 3.24 2.77

277.05 281.65 291.05 293.45 297.55 300.65 306.05 310.35 311.25 312.45

29.5 32.5 40.8 43.5 47.2 51.2 57.6 62.8 65.1 67.3

312.55 308.15 304.55 301.05 296.35 290.95 287.15 283.15

6.49 4.94 3.99 3.35 2.53 1.94 1.57 1.28

312.65 311.65 306.85 304.35 299.45 295.75 293.05 286.45 278.75

16.3 14.4 9.21 7.06 5.00 3.98 3.38 2.35 1.51

102·xNRTL cal Deionized Water 0.0146 0.0123 0.0112 0.0102 0.00915 0.00846 0.00750 0.00688 0.00573 Methanol 45.0 36.7 27.7 16.5 12.9 8.36 5.30 3.73 Ethylene Glycol 8.72 7.75 6.53 5.66 4.49 3.90 3.31 2.70 Ethyl Acetate 28.7 32.4 40.8 43.2 47.5 51.0 57.4 62.9 64.1 65.7 Hexane 6.49 5.19 4.31 3.58 2.77 2.04 1.64 1.29 Cyclohexane 16.3 15.1 10.4 8.48 5.67 4.14 3.28 1.82 0.883

a

102·xApel cal

102·xλh cal

T/K

102·xexp

102·xNRTL cal

102·xApel cal

102·xλh cal

0.0151 0.0132 0.0122 0.0113 0.0102 0.00944 0.00834 0.00761 0.00619

0.0161 0.0128 0.0116 0.0107 0.00969 0.00913 0.00841 0.00797 0.00721

313.25 307.15 303.65 299.65 295.65 288.95 284.55 280.85

65.9 56.2 49.8 44.1 39.6 31.8 27.3 25.5

Dichloromethane 65.9 55.6 50.2 44.6 39.6 32.0 27.7 24.5

66.2 55.4 50.0 44.3 39.3 32.0 27.9 24.8

65.5 55.5 50.2 44.6 39.6 32.0 27.7 24.4

52.8 42.5 36.2 30.4 27.4 24.9 65.9 45.5

68.0 62.3 53.8 42.9 36.6 31.1 26.6 24.1

66.4 44.7 34.2 27.1 21.9 17.9 8.89 6.39

63.4 46.3 35.8 28.1 22.0 17.2 6.83 4.27

52.9 38.8 28.0 21.4 16.7 11.9 7.49 5.04

50.9 38.8 28.7 22.2 17.3 12.1 7.14 4.38

59.4 39.2 25.9 14.7 9.73 5.41 3.76 2.28

56.1 40.0 27.3 15.3 9.61 4.71 2.95 1.49

77.3 61.1 49.9 40.6 31.3 25.6 20.9 77.3

78.7 61.0 49.5 40.1 31.1 25.7 21.3 78.7

45.5 36.8 27.6 16.5 13.2 8.79 5.87 4.34

44.2 36.9 28.4 17.1 13.4 8.49 5.22 3.57

313.55 310.35 305.35 298.35 293.75 289.35 285.35 282.85

69.1 62.6 52.8 42.7 35.8 30.9 27.1 24.7

8.51 7.45 6.17 5.30 4.18 3.63 3.09 2.56

8.78 7.37 5.94 5.09 4.10 3.65 3.22 2.80

315.65 309.65 305.65 302.25 299.15 296.25 286.45 281.95

66.1 45.5 34.7 26.8 21.0 17.3 9.46 6.95

315.05 311.25 307.15 303.75 300.55 296.05 289.75 284.15

54.8 37.8 25.7 20.0 16.3 13.0 9.70 7.55

29.4 32.8 40.8 43.2 47.4 50.9 57.7 63.6 64.9 66.7

29.3 32.8 40.9 43.2 47.5 51.0 57.7 63.6 64.9 66.7

6.47 4.97 4.03 3.30 2.54 1.91 1.58 1.30

6.57 4.91 3.96 3.25 2.54 1.95 1.62 1.35

316.45 312.45 308.45 302.95 298.85 292.95 289.25 284.05

61.5 37.5 22.3 14.1 11.1 8.05 6.52 5.24

15.7 14.5 9.72 7.87 5.17 3.75 2.95 1.63 0.799

15.9 14.4 9.43 7.66 5.20 3.92 3.19 1.94 1.08

318.35 311.35 305.75 300.35 294.05 289.45 285.05 318.35

76.7 62.2 49.9 40.7 31.1 25.1 21.1 76.7

Trichloromethane 69.1 62.6 53.5 42.5 36.4 31.2 27.0 24.6 Tetrachloromethane 66.1 44.6 34.1 26.9 21.6 17.5 8.41 5.89 Ethanol 54.6 42.3 31.9 25.0 19.9 14.2 8.76 5.59

Isopropanol 61.3 43.6 30.8 18.8 12.8 7.27 5.04 2.96 Benzene 76.7 59.3 47.9 38.7 29.9 24.5 20.2 76.7

Apel λh xexp, xNRTL cal , xcal , and xcal represent the experimental solubility and the solubilities calculated data using the NRTL, Apelblat, and λh models, respectively. The standard uncertainties u are u(T) = 0.1 K and u(p) ≈ 1 kPa. The relative standard uncertainty of the solubility measurements is ur(x) = 0.06. a

E



F

0.02259 321.5 3.116 −90.98 921.4 15.22 2.119 2.613 1996 2.107 −0.04246 486.9 9.453 −144.9 337.6 24.86 7.791 3.380 2675 12.13 −0.01610 329.9 7.694 −114.2 349.4 19.53 7.177 2.621 2718 10.97 0.2169 4.541 17.24 476.2 −30069 −66.38 7.956 7.019 1989 6.976

tetrachloromethane trichloromethane

0.0066 45.96 0.8786 69.85 −5793 −9.041 0.6007 1.212 2717 0.5796 0.0844 −3.533 4.784 −168.4 5091 26.38 1.776 0.9293 2905 1.344

dichloromethane cyclohexane hexane

−0.0442 135.6 18.10 −1093 45953 164.5 4.295 0.1329 16066 8.126 −0.1104 469.2 15.39 88.58 −7315 −11.51 5.222 0.6681 5060 4.482

ethyl acetate ethylene glycol methanol

λh

B′ T

Apelblat

ΔH = A′ +

−0.3845 227.7 40.23 −105.6 −880.7 18.27 12.69 0.03048 106656 3.2191

isopropanol

where τ12 and τ21 are empirical constants, α12 = α21 are related to the nonrandomness of the mixture and usually vary between 0.20 and 0.47,23 and g12 − g22 and g21 − g11 are the energy parameters. Apelblat Equation. Apelblat and co-workers thought that the enthalpy change of solution is linearly dependent on the reciprocal of the absolute temperature:24−26

−0.1613 356.5 14.73 −190.8 4438 30.03 3.194 0.00763 232178 7.059

ethanol

RT

0.1005 334.1 7.379 458.9 −236724 −68.14 2.821 −0.0001026 −0.0001026 17.02

(g21 − g11)

deionized water

RT

τ12 τ21 ARD A B C ARD λ h ARD

τ21 =

(g12 − g22)

parameter

τ12 =

model

Figure 3. Experimental mole-fraction solubilities of o-iodoaniline at p = 0.1 MPa in different solvents: ■, deionized water; ▲, methanol; ▼, ethylene glycol; ◆, ethyl acetate; ▶, hexane; ●, cyclohexane; ★, dichloromethane; ⬟, trichloromethane; +, tetrachloromethane; ×, ethanol; *, isopropanol; |, benzene. The solid lines are correlated values obtained using the Apelblat equation.

NRTL

Table 6. Parameters of the NRTL, Apelblat, and λh Models for the Solubility of p-Iodoaniline and Their Average Relative Deviations

Figure 2. Experimental mole-fraction solubilities of p-iodoaniline at p = 0.1 MPa in different solvents: ■, deionized water; ▲, methanol; ▼, ethylene glycol; ◆, ethyl acetate; ▶, hexane; ●, cyclohexane; ★, dichloromethane; ⬟, trichloromethane; +, tetrachloromethane; ×, ethanol; *, isopropanol; |, benzene. The solid lines are correlated values obtained using the Apelblat equation.

13.40 −14.49 6.874 −147.6 5168 22.73 0.4552 0.2289 2668 0.7370

benzene

Article


−0.1089 447.1 22.40 −548.8 16734 86.05 21.63 1.947 5618 28.55

0.02426 872.8 3.414 129.7 −8894 −17.71 0.9141 0.954 3655 1.493

isopropanol ethanol

0.006920 827.9 4.441 −102.5 −766.4 18.17 3.360 4.149 2113 10.70 −0.002730 330.2 0.6522 −50.02 −341.9 8.827 0.5060 1.688 2158 1.510

−0.08899 180.6 16.14 −531.7 17851 82.46 11.17 1.069 6729 14.26

tetrachloromethane trichloromethane

d ln x ΔH = dT RT 2

the empirical Apelblat equation can be derived as B + C ln T (5) T where A, B, and C are model constants. λh Equation. Buchowski et al.27 studied the relationship between the activity of the solution and the temperature and proposed the λh equation: ln x = A +

⎛1 ⎡ ⎛ 1 − x ⎞⎤ 1 ⎞ ⎟ = λh⎜ ln⎢1 + λ⎜ − ⎟ ⎥ ⎣ ⎦ ⎝ x ⎠ Tm ⎠ ⎝T

ln x = −

ΔHd ΔSd + RT R

(7)

where ΔHd and ΔSd are the enthalpy and entropy of dissolution, respectively. The average relative deviation (ARD), defined in eq 8, was used to evaluate the applicability and accuracy of the models: ARD =

1 N

N

∑ 1

xexp − xcal xexp

× 100% (8)

where xexp and xcal are the experimental and calculated solubility data, respectively, and N is the number of experimental data points. The calculated mole-fraction solubilities xcal for p-iodoaniline and o-iodoaniline are listed in Table 4 and Table 5, respectively, and the fitted model parameters and their ARD values for piodoaniline and o-iodoaniline are listed in Table 6 and Table 7, respectively. The overall ARDs for p-iodoaniline are 12.40% (NRTL), 4.501% (Apelblat), and 6.105% (λh), and those for oiodoaniline are 8.013% (NRTL), 6.085% (Apelblat), and 7.751% (λh). For most of the 24 systems, the van’t Hoff equation was found to give enthalpies of dissolution ΔHd and entropies of dissolution ΔSd with unreasonably high values (ΔHd > 15 kJ·mol−1; ΔSd > 200 J·K−1·mol−1), which showed that this equation failed in modeling the experimental data. As can be seen from Table 4 to Table 7, the NRTL model has a good correlation result for o-iodoaniline and polar organic solvent systems, while it is not so good for p-iodoaniline. The Apelblat equation always gave the best correlation results with the lowest ARD values. Besides, the solubility should have an increasing trend with increasing temperature.

4. CONCLUSIONS The solubilities of o-iodoaniline and p-iodoaniline in water, methanol, ethylene glycol, ethyl acetate, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, ethanol, isopropanol, and benzene from 273 to 333 K were measured using the laser technique. The results showed that the solubility increased with increasing temperature in all of the systems. At a given temperature, the order of solubility for oiodoaniline is water < hexane < cyclohexane ≈ ethylene glycol

λh

Apelblat

(6)

where λ and h are the two model parameters and Tm is the melting point. Van’t Hoff Equation. In the van’t Hoff equation, the logarithm of the mole-fraction solubility is linearly dependent on the reciprocal of temperature:28

−0.0006337 49.77 1.233 −57.55 243.6 9.807 1.150 1.094 2539 1.340

dichloromethane

When this is combined with the Clausius−Clapeyron equation,

−0.06474 84.27 13.63 −113.8 −1645 20.40 13.50 0.1920 29674 7.840

cyclohexane

0.007540 −4.191 0.9298 −72.56 1453 11.75 0.5540 0.6247 2530 0.5930

hexane

Article

−0.05541 310.77 4.816 −475.0 16835 72.84 0.8590 0.04481 64523 1.840

ethyl acetate

−0.06360 8.841 5.788 −145.8 3403 23.07 3.350 0.01359 53105 0.8990 0.008660 78.29 15.28 −281.8 6882 45.08 13.00 1.986 3814 17.08 0.1814 21.00 8.236 292.3 −15499 −43.76 2.290 −0.00002664 31451400 7.250 τ12 τ21 ARD A B C ARD λ h ARD

ethylene glycol methanol deionized water parameter model

NRTL

Table 7. Parameters of the NRTL, Apelblat, and λh Models for the Solubility of o-Iodoaniline and Their Average Relative Deviations

benzene


G



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< isopropanol < ethanol ≈ methanol < tetrachloromethane < benzene < trichloromethane ≈ dichloromethane < ethyl acetate, and the order for p-iodoaniline is water < hexane < cyclohexane < ethylene glycol < tetrachloromethane < isopropanol < ethanol < methanol < benzene < trichloromethane < dichloromethane < ethyl acetate. The NRTL model, Apelblat equation, λh equation, and van’t Hoff equation were employed to correlate the solubility data, and the Apelblat equation always gave the best results.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Kui Xu: 0000-0002-5887-1744 Tianxiang Li: 0000-0002-0427-8937 Funding

This project was supported by the Innovation Fund for Graduate Students of Guizhou University, China (2017009). Notes

The authors declare no competing financial interest.

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Measurement and Correlation of the Dissolution Equilibria of o

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