Determination and Correlation of Solubility of Phenylbutazone in

Jan 23, 2017 - In this paper, we focused on the solubility of phenylbutazone, which was characterized by FT-IR spectra and X-ray diffraction. By the m...
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Determination and Correlation of Solubility of Phenylbutazone in Monosolvents and Binary Solvent Mixtures Aizhen Liang, Shui Wang, and Yixin Qu* Beijing Key Laboratory of Membrane Science and Technology, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, People’s Republic of China S Supporting Information *

ABSTRACT: In this paper, we focused on the solubility of phenylbutazone, which was characterized by FT-IR spectra and X-ray diffraction. By the method of a laser technique, the solubility of phenylbutazone was measured in 10 monosolvents (methanol, ethanol, 2-propanol, n-butanol, 1-pentanol, n-hexanol, acetonitrile, ethyl acetate, acetone, and DMF) and 2 binary solvent mixtures of methanol + acetone and ethanol + acetonitrile from 283 to 323 K at about 5 K intervals under atmospheric pressure. The results show that the solubility of phenylbutazone in monosolvents and mixed solvents increases with the increase of temperature. However, it decreases with the increasing initial mole fraction of alcohols in the selected mixed solvents at constant temperature. The experimental data were correlated by the modified three-parameter van’t Hoff equation and the modified Jouyban−Acree equation.

1. INTRODUCTION Phenylbutazone (PBZ, C19H20N2O2, CAS registry no: 50-33-9), which is known as 4-butyl-1,2-diphenyl-3,5-pyrazolidinedione, is used as a nonsteroidal anti-inflammatory drug (NSAID) in veterinary medicine including food producing animals. It was mainly used in the treatment of rheumatoid arthritis, ankylosing spondylitis. PBZ has a good effect on inflammatory pain, and its effect is similar to amidopyrine. Because of its antipiretic, analgesic, and anti-inflammatory effects, it has brought major welfare benefits to horses as an analgesic/anti-inflammatory agent for over more than 50 years of clinical use.1 The chemical structure of PBZ is shown in Figure 1. It was reported that there were four polymorphs of PBZ.2 The measured solubility data of PBZ is the data of stable polymorph IV in our work.

equilibrium solubility that varies with temperature and solution composition. During crystallization process, the supersaturation of a solution has a direct effect on the quality of the resulting crystals. In order to optimize the crystallization process and make good use of PBZ, solubility data are necessary for the thermodynamics and kinetics investigation during the crystallization. However, few studies have investigated the solubility of PBZ so far. In this work, the method of laser technique was used to determine the solubility of PBZ in 10 monosolvents (methanol, ethanol, 2-propanol, n-butanol, 1-pentanol, n-hexanol, acetonitrile, ethyl acetate, acetone, and DMF) and 2 binary solvents mixtures of methanol + acetone and ethanol + acetonitrile from 283 to 323 K at about 5 K intervals under atmospheric pressure. The modified three-parameter van’t Hoff equation and the modified Jouyban−Acree (J-A) equation were used to correlate the experimental data.

2. EXPERIMENTAL SECTION 2.1. Materials and Reagents. PBZ (white powder, mass fraction purity >0.997) was purchased from Energy Chemical of Sun Chemical Technology (Shanghai) Co., Ltd. All solvents used for experiments were in analytical reagent grade and their mass fraction was higher than 99.5%. More detailed information about materials and reagents used in this work is given in Table 1. 2.2. Characterization by FT-IR Spectra. The FT-IR spectra of PBZ (Form IV) was recorded by using the KBr

Figure 1. Chemical structure of PBZ.

Until now, due to the commercial and medicinal sense, PBZ has attracted considerable attention focusing on its bioavailability and synthesis but little attention has been paid to the purification and crystallization of crystals for further production of PBZ.3 Crystallization is an important step in industrial purification processes, and it strongly relies on accurate © 2017 American Chemical Society

Received: October 27, 2016 Accepted: January 12, 2017 Published: January 23, 2017 864

DOI: 10.1021/acs.jced.6b00911 J. Chem. Eng. Data 2017, 62, 864−871

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2926.39, 2872.51, and 2859.18 cm−1 are the C−H stretching vibration absorption for n-butyl group. The band at 1433.89 cm−1 is the CH bending vibration absorption for n-butyl group. We can draw the conclusion from these characteristic peaks that the material determined was just PBZ. 2.3. Characterization by X-ray Diffraction. The powder X-ray diffraction (PXRD) of PBZ (Form IV) was performed to identify the crystal form used in the experiment. The PXRD patterns were obtained by XRD-6000 at room temperature and by using Cu KR radiation of wavelength 0.154060 nm at a tube voltage of 40 kV and a tube current of 40 mA. The measurements were carried out over a diffraction-angle (2θ) range from 3° to 50° at a step size of 0.01° with a scanning rate of 0.1s/step. The X-ray power diffraction (XPRD) patterns of PBZ are shown in Figure 3. It can be seen that there are two distinct characteristic peaks at 8.06° and 20.92°, respectively.

Table 1. Description of the Materials Used in the Experiments

chemical name

initial mass fraction purity

purification method

phenylbutazone (PBZ)

>0.997

none

methanol

>0.995

none

ethanol

>0.997

none

2-propanol

>0.995

none

n-butanol

>0.995

none

n-pentanol

>0.995

none

n-hexanol

>0.995

none

acetonitrile

>0.995

none

ethyl acetate

>0.995

none

acetone

>0.995

none

DMF

>0.995

none

a

analysis method HPLC

a

source Energy Chemical of Sun Chemical Technology (Shanghai) Co., Ltd. Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Tianjin Fuchen Chemical Reagents Factory Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China Beijing Chemical Co., Ltd. of China

High-performance liquid chromatography.

pressed pellets, and a FT-IR Spectrometer (Nicoiet 8700) with a deuterated triglycine sulfate (DTGS) detector at 4 cm−1 intervals over the spectral range from 400 to 4000 cm−1. The FT-IR spectrum of PBZ was shown in Figure 2. In the FT-IR spectrum of PBZ, the CH stretching vibration absorption peaks for phenyl rings are observed at 3059.90 and 3049.91 cm−1. The peaks at 1595.74 and 1488.78 cm−1 are the CC skeleton stretching vibration absorption for phenyl rings. The CH out-of-plane bending vibration absorption for phenyl rings are shown at 754.55, 703.64, and 694.37 cm−1. The two strong bands at 1752.15 and 1716.81 cm−1 are the CO stretching vibration absorption. The observed bands at 1297.56, 1195.88, and 1154.20 cm−1 are the C−N stretching vibration absorption. The bands at 2957.15,

Figure 3. X-ray power diffraction patterns of PBZ.

2.4. Apparatus and Procedure. In this work, the solubility of PBZ was measured at atmospheric pressure by using an apparatus which is similar to the one described in literature.4

Figure 2. FT-IR spectrum of PBZ. 865

DOI: 10.1021/acs.jced.6b00911 J. Chem. Eng. Data 2017, 62, 864−871

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Table 2. Experimental and Calculated Mole Fraction Solubility x of PBZ in Monosolvents at Temperature T and Pressure P = 101 kPaa,b,c,d T/K

103x1

103x1c

T/K

100RD

103x1

methanol 283.12 288.03 293.13 298.16 303.14 308.15 313.15 318.15 323.15

4.20 5.18 6.54 8.31 10.73 14.14 18.90 26.14 37.72

283.15 288.15 293.05 298.15 303.90 308.15 313.13 318.65 323.15

2.49 3.02 4.03 5.62 8.19 10.94 16.46 25.41 39.80

283.15 288.15 293.12 298.11 303.15 308.15 313.15 318.13 323.16

4.12 5.39 6.93 8.85 12.11 16.54 22.10 32.00 48.14

283.12 288.15 293.15 298.17 303.15 308.13 313.10 318.17 323.16

33.67 45.68 63.17 89.52 111.99 136.45 164.05 194.14 225.40

283.15 288.13 293.15 298.17 303.15 308.13 313.15 318.15 323.15

70.53 82.81 96.64 113.21 132.58 153.25 176.31 201.17 226.16

103x1c

100RD

4.27 4.88 5.93 7.45 9.70 13.04 18.07 25.48 36.87

−7.79 −3.37 1.94 3.68 2.99 1.39 −1.57 −1.49 0.61

4.29 5.35 6.87 9.05 12.21 16.79 23.51 33.44 48.23

−5.14 1.02 2.22 0.94 0.22 −0.94 0.45 −0.33 0.10

3.47 4.70 6.45 8.97 12.45 17.33 24.20 33.87 47.47

11.96 −0.64 −2.08 −6.22 0.65 1.60 −1.30 1.12 −0.32

63.96 75.71 89.30 104.87 122.89 143.43 167.94 194.29 223.69

−0.24 0.99 0.42 −0.75 −0.92 −0.07 0.65 0.32 −0.31

114.60 130.29 147.43 166.07 186.53 208.63 232.54 260.74 286.18

−0.33 0.14 −0.02 0.23 0.18 −0.09 0.00 −0.39 0.24

ethanol 4.54 5.24 6.42 8.11 10.51 14.00 19.07 26.51 37.51

−8.13 −1.12 1.78 2.45 2.05 1.01 −0.92 −1.40 0.55

283.13 288.10 293.20 298.15 303.15 308.15 313.20 318.15 323.15

3.96 4.72 6.05 7.73 10.00 13.22 17.79 25.11 37.09

2.67 3.21 4.05 5.41 7.93 10.86 16.19 26.12 39.52

−7.28 −6.11 −0.34 3.62 3.15 0.78 1.64 −2.79 0.71

283.14 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

4.08 5.41 7.03 9.14 12.23 16.64 23.62 33.33 48.28

4.55 5.44 6.77 8.74 11.68 16.03 22.58 32.48 47.86

−10.55 −1.00 2.28 1.25 3.52 3.04 −2.19 −1.51 0.60

283.15 288.05 293.05 298.15 303.15 308.15 313.15 318.15 323.15

3.94 4.67 6.32 8.45 12.53 17.61 23.89 34.26 47.32

33.17 47.46 65.14 86.31 110.40 137.02 165.35 195.15 224.36

1.51 −3.90 −3.11 3.58 1.42 −0.41 −0.79 −0.52 0.46

283.15 288.15 293.15 298.13 303.15 308.15 313.37 318.30 323.17

63.80 76.47 89.67 104.10 121.77 143.33 169.04 194.90 223.01

69.56 82.65 97.54 114.23 132.66 153.03 175.63 200.25 227.05

1.37 0.19 −0.93 −0.90 −0.06 0.14 0.39 0.46 −0.39

283.13 288.15 293.15 298.13 303.15 308.15 313.15 318.60 323.17

114.22 130.47 147.40 166.46 186.87 208.44 232.54 259.74 286.88

n-butanol

2-propanol

n-pentanol

n-hexanol

acetonitrile

ethyl acetate

acetone

DMF

a

Standard uncertainties u are u(T) = 0.05 K, u(P) = 5 KPa, ur(x1) = 0.03. bx1 is experimental solubility data of PBZ. cx1c represents the calculated solubility data by the modified three-parameter van’t Hoff equation. dRD refers to the corresponding relative deviation.

mercury-in-glass thermometer (uncertainty of ±0.05 K) was inserted into the inner cell of the vessel to measure the solution temperature. The solute of PBZ was batch-type added into the cell and the mass of every batch was written down. The mass of the solute and solvents was weighed using an analytical balance (SartoriousBT423S, Germany) (uncertainty of ±0.0001 g).

It contains two parts: one consists of a laser generator, a photoelectric transformer, and a light intensity recorder and the other is the solubility apparatus. The dissolution of the solute was carried out in a jacketed glass vessel that was maintained at a desired temperature by circulated water from a water batch with a thermoelectric controller (type 501, China). A calibrated 866

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Table 3. Experimental and Calculated Mole Fraction Solubility x of PBZ in Binary Solvent Mixtures of Methanol (3) + Acetone (2) at Temperature T and Pressure P = 101 kPaa,b,c,d,e T/K

103x1

103x1c x20

283.12 288.03 293.13 298.16 303.14 308.15 313.15 318.15 323.15

4.20 5.18 6.54 8.31 10.73 14.14 18.90 26.14 37.72

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.27 323.17

7.73 9.54 11.64 14.69 18.97 25.09 33.76 47.31 67.55

283.15 288.15 293.12 298.15 303.15 308.15 313.15 318.15 323.15

12.58 15.32 18.96 24.11 31.11 40.77 54.39 73.94 101.15

T/K

100RD

103x1

4.00 4.91 6.24 8.09 10.68 14.41 19.80 27.65 39.25

4.76 5.20 4.52 2.65 0.43 −1.92 −4.76 −5.79 −4.07

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

43.21 52.22 63.24 76.40 92.43 112.48 136.21 163.05 185.78

7.73 9.46 11.81 15.05 19.53 25.77 34.55 47.35 64.87

−0.01 0.84 −1.51 −2.45 −2.96 −2.74 −2.33 −0.07 3.97

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

51.51 62.19 74.37 88.78 106.47 127.69 152.34 179.66 208.53

13.00 15.80 19.52 24.57 31.35 40.58 53.20 70.59 94.71

−3.30 −3.11 −2.91 −1.89 −0.79 0.46 2.19 4.53 6.37

283.15 288.13 293.16 298.15 303.13 308.15 313.28 318.13 323.23

59.28 70.67 84.10 100.06 119.14 141.27 166.58 192.90 219.81

26.65 32.62 40.12 49.54 61.67 78.11 99.89 128.06 155.90

283.15 288.17 293.15 298.15 303.16 308.15 313.15 318.15 323.15

34.99 42.67 51.85 63.18 77.61 96.01 118.38 144.80 172.95

−0.45 0.03 0.45 0.41 0.33 0.65 0.33 −1.28 −8.25

51.33 61.73 74.13 88.90 106.46 127.30 151.99 181.23 215.77

0.35 0.74 0.32 −0.13 0.01 0.31 0.23 −0.87 −3.47

58.42 70.23 84.14 100.16 118.62 140.05 165.19 192.34 224.79

1.46 0.63 −0.04 −0.10 0.44 0.86 0.83 0.29 −2.27

64.32 77.54 92.56 109.44 128.56 149.64 173.17 198.75 226.70

2.10 0.39 −0.61 −1.18 −0.70 0.11 1.00 1.55 1.63

68.74 82.84 98.68 116.12 134.91 155.06 176.59 199.08 222.39

2.54 −0.04 −2.11 −2.57 −1.75 −1.18 −0.16 1.04 1.66

x20 = 0.8007

x20 = 0.3000

283.13 288.15 293.15 298.15 303.15 308.15 313.23 318.65 323.15

43.40 52.21 62.95 76.08 92.13 111.75 135.75 165.13 201.10 x20 = 0.7019

x20 = 0.1999

18.85 23.37 28.84 35.94 45.90 58.80 76.42 99.25 128.46

100RD

x2 = 0.6006

= 0.0000

x20 = 0.1002

283.15 288.15 293.15 298.15 303.17 308.15 313.15 318.13 323.15

103x1c 0

x20 = 0.8991 19.63 23.75 29.14 36.21 45.57 57.88 74.33 96.25 125.99

−4.14 −1.63 −1.03 −0.75 0.72 1.58 2.74 3.03 1.92

283.12 288.15 293.16 298.14 303.17 308.15 313.18 318.16 323.15

65.70 77.84 92.00 108.16 127.66 149.80 174.92 201.88 230.47

27.24 32.88 40.06 49.27 61.11 76.40 96.58 124.96 155.62

−2.19 −0.79 0.14 0.55 0.91 2.19 3.31 2.42 0.17

283.15 288.13 293.15 298.17 303.15 308.13 313.15 318.15 323.15

70.53 82.81 96.64 113.21 132.58 153.25 176.31 201.17 226.16

35.30 42.53 51.50 62.75 76.91 94.63 117.00 145.25 180.97

−0.89 0.33 0.69 0.67 0.90 1.43 1.17 −0.31 −4.64

x20 = 0.4008

x20 = 1.0000

x20 = 0.5008

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Table 3. continued a

Standard uncertainties u are u(T) = 0.05 K, u(P) = 5 KPa, ur(x1) = 0.03. bx1 is the mole fraction of PBZ in the binary solvent mixture. cx1c represents the calculated solubility data by the modified Jouyban-Acree model. dRD refers to the corresponding relative deviation. ex20 represents the initial mole fraction of acetone in (methanol + acetone) mixed solvents.

solubility of PBZ, the new hybrid Jouyban-Acree model was applied to correlate the solubility in two binary solvents at different temperatures, which is a combination of Jouyban− Acree model and the modified Apelblat equation, and can be expressed as follows9

The dissolution of the solute was examined by the laser beam penetrating the vessel, which was continuously stirred by a magnetic stir bar. As the solute gradually dissolved, the light intensity continuously increased. When the solute dissolved completely, the light intensity reached the maximum. Then additional PBZ solute of known mass (about 0.5−5 mg) was introduced into the vessel. This procedure was repeated until the last added solute could not be dissolved completely for about 30 min, that is to say, the penetrated laser intensity could not achieve the maximum again. Thus, the total mass dissolved can be determined, and the corresponding solubility can be obtained.5 The same solubility experiment was repeated three times, and the average was used to calculate the mole fraction solubility of PBZ x1 according to eq 1. The initial composition of the solvent mixture x20 was defined in eq 2 x1 =

x 20

=

N

ln x1 = x 2 ln(x1)2 + x3 ln(x1)3 + x 2x3 ∑ i=0

n

+ ∑i = 2

mi Mi

where x1 is the mole fraction solubility of solute and x2 and x3 refer to mole fraction on solute free basis. Ji is the model constant, T is the absolute temperature, and N can be equal to 0, 1, 2 and 3, respectively. Depending on the values of N, four equations can be obtained from eq 4. (x1)i is the molar fraction solubility of the solute in monosolvents i. The others considered the (x1)i as a constant. In fact, the solubility of solute in the monosolvent systems will also vary with temperature. Therefore, it would make a mistake to some extent. In our work, considering the deviation resulted by the Apelblat model was very small, we can take the place of the ln(x1)i by the Apelblat model

(1)

m2 M2 m2 M2

+

m3 M3

(2)

where ms and MS represent the mass and the molecular weight of the solute respectively, and mi and Mi represent the mass and the molecular weight of solvent, respectively. In this work, n = 2 or 3 separately means the single solvent and mixed solvents. In methanol + acetone mixed solvents, m2, m3 represent the mass of acetone and methanol, respectively; M2, M3 represent the molecular weight of acetone and methanol, respectively. In ethanol + acetonitrile mixed solvents, m2, m3 represent the mass of ethanol and acetonitrile, respectively; M2, M3 represent the molecular weight of ethanol and acetonitrile, respectively. On the basis of Noyess−Whitney equation and Freundlich− Ostwald equation, it is better to mill the solute initially to make the measurement more efficient and the results more accurate.4

b c + T /K (T /K)2

ln(x1)2 = a1 +

b1 + c1 ln T T

(5)

ln(x1)3 = a 2 +

b2 + c 2 ln T T

(6)

When N = 2, substituting (1 − x3) with x2 for the binary solvent mixtures, the J-A model can be described as b1 x + c1 ln T + (a1 − a 2)x 2 + (b1 − b2 + J0 − J1 + J2 ) 2 T T x22 x23 x2 4 + (3J1 − J0 − 5J2 ) + (8J2 − 2J1) + (− 4J2 ) T T T

ln x1 = a1 +

(7)

+ (c1 − c 2)x 2 ln T

Here proposing several constant terms, eq 7 can be further simplified as eq 8

3. MODELS OF SOLUBILITY DATA In order to describe the dependency of the solubility of PBZ on the temperature in different monosolvents and binary solvent mixtures, the following two models were used to correlate the data in this work. 3.1. Modified Three-Parameter van’t Hoff Equation. The van’t Hoff equation reflects the relationship between the mole fraction solubility of solute and the temperature in a real solution, which is expressed as eq 3 ln x1 = a +

T (4)

ms Ms ms Ms

Ji (x 2 − x3)i

A2 x x 2 x 3 + A3 ln T + A4 x 2 + A5 2 + A 6 2 + A 7 2 T T T T x2 4 + A8 + A 9x 2 ln T T

ln x1 = A1 +

(8)

where A1 to A9 are model parameters. The model was used to correlate experimental solubility data of mixed solvents in this work.

4. RESULTS AND DISCUSSION 4.1. Solubility Data. The experimental data in monosolvents are listed in Table 2 and are also graphically shown in Figure S1 of the Supporting Information. It can be found that the solubility of PBZ is a function of temperature and increases with the increase of temperature in monosolvents. It is obvious that the PBZ shows the highest solubility in DMF but relatively low solubility in alcohols solvents. The order of mole fraction solubility of PBZ in the experimental temperature range is DMF > acetone > ethyl acetate > acetonitrile > alcohols. There

(3)

where x1 is the mole fraction solubility of solute and a, b, and c are empirical parameters, which could be regressed from the experimental solubility data by multivariable linear-least-squares method. The model was used to correlate experimental solubility data of monosolvents in this work.6−8 3.2. Modified Jouyban−Acree model. Considering the effect of both temperature and solvent composition on the 868

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Table 4. Experimental and Calculated Mole Fraction Solubility x of PBZ in Binary Solvent Mixtures of Ethanol (2) + Acetonitrile (3) at Temperature T and Pressure P = 101 kPaa,b,c,d,e T/K

103x1

103x1c x20

283.12 288.15 293.15 298.17 303.15 308.13 313.10 318.17 323.16

33.67 45.68 63.17 89.52 111.99 136.45 164.05 194.14 225.40

283.13 288.11 293.15 298.35 303.15 308.15 313.25 318.15 323.15

42.76 56.25 76.00 95.63 115.54 138.98 165.91 194.69 225.32

283.13 288.15 293.16 298.15 303.14 308.13 313.15 318.15 323.16

45.99 63.25 76.42 94.89 116.67 141.64 169.61 199.12 229.60

T/K

100RD

103x1 x20

= 0.0000 38.57 52.36 68.67 87.41 107.94 129.76 152.06 174.48 195.31

−14.55 −14.63 −8.70 2.35 3.62 4.91 7.31 10.13 13.35

283.15 288.15 293.20 298.15 303.15 308.15 313.15 318.15 323.15

29.51 37.16 46.01 57.01 71.15 89.45 112.33 139.52 171.35

43.76 58.12 75.46 96.26 117.89 142.57 169.48 196.40 224.25

−2.32 −3.33 0.71 −0.66 −2.04 −2.58 −2.15 −0.88 0.48

283.15 288.32 293.15 298.15 303.15 308.15 313.15 318.15 323.15

22.52 27.90 34.44 43.04 54.32 69.37 89.22 114.84 146.28

44.80 58.76 75.48 95.02 117.50 142.87 171.15 201.82 234.70

2.57 7.10 1.23 −0.14 −0.71 −0.87 −0.91 −1.36 −2.22

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

14.56 18.39 23.01 28.93 36.83 47.84 63.00 83.58 112.59

x20 = 0.1076

283.12 288.20 293.13 298.15 303.15 308.11 313.15 318.15 323.22

44.00 54.18 66.08 80.81 99.00 120.88 146.31 175.25 207.54

283.15 288.15 293.15 298.20 303.15 308.15 313.15 318.15 323.16

36.72 46.13 56.76 69.76 86.28 106.89 131.95 161.37 194.39

29.47 36.56 45.62 56.88 71.30 89.63 112.96 142.69 180.60

0.11 1.62 0.85 0.23 −0.22 −0.20 −0.56 −2.27 −5.40

22.68 28.03 34.48 43.11 54.36 69.06 88.36 113.80 147.43

−0.72 −0.48 −0.11 −0.16 −0.06 0.45 0.96 0.91 −0.79

15.42 18.75 23.16 29.03 36.88 47.45 61.75 81.24 107.93

−5.86 −1.94 −0.67 −0.34 −0.14 0.82 1.97 2.80 4.13

8.85 10.71 13.23 16.67 21.40 27.95 37.09 49.95 68.19

−6.41 −1.63 −0.12 0.47 0.90 1.21 1.64 2.57 6.78

4.04 4.87 6.06 7.69 10.01 13.32 18.14 25.00 35.18

−2.01 −3.12 −0.25 0.50 −0.13 −0.76 −1.97 0.43 5.14

x20 = 0.8024

x20 = 0.2988 48.56 61.34 74.23 89.78 109.45 132.58 158.98 187.56 218.68

100RD

= 0.6019

x20 = 0.7017

x20 = 0.2006

283.13 288.47 293.20 298.13 303.15 308.15 313.15 318.15 323.15

103x1c

x20 = 0.9016 43.36 56.94 71.50 89.49 111.04 136.01 164.71 197.32 234.00

10.71 7.17 3.68 0.32 −1.45 −2.58 −3.60 −5.21 −7.01

283.13 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

8.32 10.54 13.22 16.75 21.60 28.29 37.71 51.26 73.15

39.98 51.08 64.27 80.58 100.19 123.50 151.71 184.88 224.54

9.15 5.72 2.74 0.29 −1.20 −2.17 −3.69 −5.50 −8.19

283.13 288.10 293.20 298.15 303.15 308.15 313.20 318.15 323.15

3.96 4.72 6.05 7.73 10.00 13.22 17.79 25.11 37.09

35.30 44.33 55.55 69.62 86.69 107.96 134.18 166.43 206.11

3.86 3.90 2.13 0.20 −0.47 −1.00 −1.69 −3.14 −6.03

x20 = 0.4005

x20 = 1.0000

x20 = 0.5018

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DOI: 10.1021/acs.jced.6b00911 J. Chem. Eng. Data 2017, 62, 864−871

Journal of Chemical & Engineering Data

Article

Table 4. continued a

Standard uncertainties u are u(T) = 0.05 K, u(P) = 5 KPa, ur(x1) = 0.03. bx1 is the mole fraction of PBZ in the binary solvent mixture. cx1c represents the calculated solubility data by the modified Jouyban-Acree model. dRD refers to the corresponding relative deviation. ex20 represents the initial mole fraction of ethanol in (ethanol + acetonitrile) mixed solvents.

Table 5. Parameters of the Three-Parameter van’t Hoff Equation for the Solubility of PBZ in Monosolvents at Pressure P = 101 kPaa,b

a

solvent

a

b

c

RAD %

104 RMSD

methanol ethanol 2-propanol n-butanol n-pentanol n-hexanol acetonitrile ethyl acetate acetone DMF

75.70 86.07 107.76 70.13 85.11 42.36 −29.97 10.56 3.43 5.37

−43624.63 −49841.82 −61888.71 −39507.97 −48730.11 −22289.52 21088.41 −4802.20 −605.36 −2181.71

5849220.04 6773316.38 8409267.40 5126943.93 6542235.97 2460724.73 −3841662.69 292698.52 −317028.99 13630.64

2.16 2.76 2.94 1.26 2.88 2.88 1.75 0.52 0.54 0.18

2.12 2.53 3.05 1.20 3.67 3.11 16.41 7.22 7.43 4.69

Standard uncertainties u is u(P) = 5 KPa. ba, b, and c are parameters of the three-parameter van’t Hoff equation.

acetonitrile available for cooling crystallization of PBZ. Furthermore, the experimental data have been compared with the literature data graphically in Figure S2. We can see that the experimental solubility data of PBZ in the monosolvent of ethanol agree closely with those reported by the literature.10 The small deviation between them could be a result of comprehensive effects of several factors, including the errors of different solubility measurements, reservation of significant digits, the different temperature points, the reading errors of temperature, weighing errors of solute and solvent, and so forth. In this work, the solubility of PBZ in methanol + acetone and ethanol + acetonitrile mixed solvents was measured. The solubility values in binary solvent mixtures within the temperature range are listed in Tables 3 and 4 and are graphically shown in Figures S3 and S4, respectively. It can be found that the solubility of PBZ increases with increasing temperature in the two binary solvent mixtures. It also increases with the increasing initial mole fraction of acetone in mixed solvents of methanol + acetone while it decreases with increasing initial mole fraction of ethanol in mixed solvents of ethanol + acetonitrile at a given temperature. This experimental phenomenon attributes to the principal of ‘“like dissolves like”’.11 We can know from Figure S1 that the dissolving capacity of PBZ in acetone was much higher than in methanol, so the solubility of PBZ would increases with the increasing initial component of acetone in methanol + acetone mixed solvents. Similarly, in ethanol + acetonitrile mixed solvents, the solubility of PBZ decreases with the increasing initial component with lower dissolving ability solvent (ethanol). 4.2. Evaluation of Data Correlation by the Models. To evaluate the data correlation of the above-mentioned models, the relative deviation (RD), relative average deviation (RAD) and root-mean-square deviation (RMSD) were employed to measure the accuracy and predictability of various models.12,13 The RD, RAD, and RMSD can be calculated by eqs 9−11, respectively

Table 6. Parameters of the Modified Jouyban-Acree Model for the Solubility of PBZ in Binary Solvent Systems of Methanol (3) and Acetone (2) at PresSure P = 101 kPaa,b parameters

value

A1 A2 A3 A4 A5 A6 A7 A8 A9 RAD % 104 RMSD

−710.10 27330.92 107.70 866.34 −35465.85 −2378.24 1595.96 −496.55 −129.96 1.67 24.31

P-value 1.81 9.41 5.01 4.10 1.08 2.30 3.04 8.10 2.71

× × × × × × × × ×

10−32 10−28 10−33 10−23 10−20 10−26 10−09 10−05 10−23

a

Standard uncertainties u is u(P) = 5 KPa. bA1 to A9 are parameters of the modified Jouyban-Acree model.

Table 7. Parameters of the Modified Jouyban−Acree Model for the Solubility of PBZ in Binary Solvent Systems of Ethanol (2) and Acetonitrile (3) at Pressure P = 101 kPaa,b parameters

value

A1 A2 A3 A4 A5 A6 A7 A8 A9 RAD % 104 RMSD

514.45 −26425.40 −75.16 −1260.32 56744.61 −1902.16 2385.27 −1631.49 188.05 2.88 54.28

P-value 1.88 1.62 3.58 3.68 3.77 3.81 7.86 1.05 3.42

× × × × × × × × ×

10−10 10−12 10−10 10−17 10−17 10−09 10−07 10−10 10−17

a Standard uncertainties u is u(P) = 5 KPa. bA1 to A9 are parameters of the modified Jouyban−Acree model.

are no certain rules of the order in alcohols solvents, and some intersections can be seen from the solubility curves of PBZ in alcohols. In addition, its solubility in acetonitrile shows the strongest positive dependency on temperature that makes

RD = 870

xi − xic xi

(9) DOI: 10.1021/acs.jced.6b00911 J. Chem. Eng. Data 2017, 62, 864−871

Journal of Chemical & Engineering Data RAD% =

100 N

N

∑ i=1

xic − xi xi

⎡ ∑N (x c − x )2 ⎤1/2 i i ⎥ RMSD = ⎢ i = 1 ⎢⎣ ⎥⎦ N

Article

Notes

The authors declare no competing financial interest.

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(10)

(11)

where N is the number of experimental points, xic and xi represent the calculated and experimental mole fraction solubility of PBZ, respectively. The modified three-parameter van’t Hoff equation was used to correlate the solubility of PBZ in all monosolvents. The parameters of the equation for the solubility of PBZ in monosolvents are listed in Table 5. It indicated that the solubility data of PBZ calculated by the model showed good agreement, thus the modified three-parameter van’t Hoff equation is suitable for correlating the solubility data of PBZ in the selected monosolvents. In addition, it can be drawn from Table 2 that most of the absolute values of relative deviations do not exceed 10%, which demonstrates the reliability of the experimental points. The modified Jouyban−Acree model was applied to correlate the solubility of PBZ in the mixtures of methanol + acetone and ethanol + acetonitrile. The parameters of the model in mixed solvents are given in Tables 6 and 7, respectively. It can be seen that the solubility of PBZ was well-correlated by the modified Jouyban−Acree model. All of the RAD % values were less than 3%, indicating the accuracy and reliability of the model in binary solvent mixtures. Moreover, all the P-values that fitted by the modified Jouyban−Acree model were less than 0.05, which indicates the dependability of the parameters.

5. CONCLUSIONS In this work, the solubility of PBZ (Form IV) in 10 monosolvents and 2 binary solvent mixtures of methanol + acetone and ethanol + acetonitrile were determined by the method of laser technique under atmospheric pressure. The solubility of PBZ is a function of temperature and solvent composition and increases with the increasing of temperature in both monosolvents and binary solvent mixtures. However, it decreases with the increasing initial mole fraction of alcohols in the selected mixed solvents at constant temperature. The order of mole fraction solubility of PBZ in the experimental temperature range is DMF > acetone > ethyl acetate > acetonitrile > alcohols. The models applied in this paper are all suitable for correlating the solubility data of PBZ, and all of them can be used to evaluate the experimental data.

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REFERENCES

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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.6b00911. Solubility curves of PBZ in monosolvents and binary solvent mixtures (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Yixin Qu: 0000-0001-6343-0217 871

DOI: 10.1021/acs.jced.6b00911 J. Chem. Eng. Data 2017, 62, 864−871