Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Solubility and Preferential Solvation of 3‑Nitrobenzonitrile in Binary Solvent Mixtures of Ethyl Acetate Plus (Methanol, Ethanol, n‑Propanol, and Isopropyl Alcohol) Min Zheng,† Jiao Chen,† Renjie Xu,‡ Gaoquan Chen,† Yang Cong,† and Hongkun Zhao*,† †
College of Chemistry & Chemical Engineering, and ‡Guangling College, YangZhou University, YangZhou, Jiangsu 225002, People’s Republic of China S Supporting Information *
ABSTRACT: The solubilities of 3-nitrobenzonitrile in solvent mixtures of ethyl acetate (1) + methanol (ethanol, n-propanol or isopropyl alcohol) (2) determined over the temperature range from 278.15 to 318.15 K under atmospheric pressure (101.1 kPa) with the isothermal dissolution equilibrium method were reported. They increased with a rise of temperature and mass fraction of ethyl acetate, and the largest solubility value was observed in neat ethyl acetate for all the binary mixtures investigated. The temperature and solvent composition dependence of 3-nitrobenzonitrile solubility was analyzed through the Jouyban−Acree, van’t Hoff− Jouyban−Acree, and Apelblat−Jouyban−Acree models acquiring average relative deviations lower than 1.57% and root-mean-square deviation lower than 11.52 × 10−4 for correlative investigations. In addition, the preferential solvation parameters (δx1,3) of 3-nitrobenzonitrile by ethyl acetate were determined from experimental solubility values by using the inverse Kirkwood−Buff integrals. It was found that alcohol preferentially solvated 3-nitrobenzonitrile in alcohol-rich mixtures while ethyl acetate forms local solvation shells in compositions from intermediate composition up to neat ethyl acetate. The former case was possibly due to the ordered structure of alcohol molecules around the apolar group of 3-nitrobenzonitrile, which was formed via hydrophobic hydration in alcohol-rich solutions.
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chemical, pharmaceutical, petrochemical, food, and material.16,17 The solubility of solids in mixed solvents as a function of temperature and composition is very important in understanding the solid−liquid equilibrium in the development of a crystallization process and performing further thermodynamic investigation. So the solubility of 3-nitrobenzonitrile is very important in the purification process of 4-nitrobenzonitrile using solvent crystallization. Recently, we reported the solubility of 3-nitrobenzonitrile in 12 neat solvents (ethanol, methanol, n-propanol, acetone, isopropyl alcohol, 2-methyl-1-propanol, n-butanol, acetic acid, acetonitrile, cyclohexane, ethyl acetate, and toluene determined using the static method at temperatures ranging from (278.15 to 318.15) K.18 As is known to all, solvent mixing with temperature adjustment is a usual way to alter the solubility of solids in crystallization investigations. Information of the solubility in mixed solvents enables discovering the suitable solvent system for purification of 4-nitrobenzonitrile. On the basis of our previous study,18 the 3-nitrobenzonitrile solubility is greater in ethyl acetate than in alcohols. The mixed solvents may alter the solubility of 3-nitrobenzonitrile. To enrich the solubility database and choose a suitable solvent system, as a continuation of our previous work,
INTRODUCTION Isomer separation is attracting worldwide attention because of its high scientific importance and demands in the chemical industry. However, it is not successfully achieved through the distillation method because of the close boiling points of pairs in a mixture.1 Purification of the isomers can also be made by several other methods, for example, adsorption,2,3 adjusting pH values,4 chemical conversion,5 pervaporation,6 and so on. Contrary to the solvent crystallization method, the above techniques are very complex and energy-expensive. 3-Nitrobenzonitrile (CAS Registry No. 619-24-9, chemical structure shown in Figure S1 of the Supporting Information) is used commercially as an intermediate in choleretic and antispasmodic drugs.7 It is a byproduct in the production of 4-nitrobenzonitrile by nitration of benzonitrile using HNO3 or another nitrating agent in the presence of a catalyst.8−13 The isomeric byproduct restricts further uses of 4-nitrobenzonitrile in many fields. With the improvement of dyestuff and the pharmaceutical industry, the demand for purity of 4-nitrobenzonitrile is increasing. Therefore, it is a very important step to remove isomeric 3-nitrobenzonitrile from crude nitration products. In recent years, solvent crystallization has been successfully applied to separate organic isomers.14,15 It is well-known that solubility is a significant thermodynamic property. It can offer required information for the design and optimization of the purification and separation process in various areas such as © XXXX American Chemical Society
Received: March 22, 2018 Accepted: May 22, 2018
A
DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 1. Detailed Description of 3-Nitrobenzonitrile and the Selected Solvents chemicals
molar mass g·mol−1
density kg·m−3 (295 K)
3-nitrobenzonitrile
148.12
1310a
methanol
32.04
ethanol n-propanol isopropyl alcohol ethyl acetate
46.07 60.06 60.06 88.11
a
source
initial mass fraction purity
purification method
final mass fraction purity
analytical method
0.970
recrystallization
0.996
HPLCb
0.997
0.993
GCc
0.995 0.993 0.994 0.995
0.995 0.994 0.994 0.995
GC GC GC GC
Shangdong Shuojia Chemical Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd.,China
Taken from ref 18. bHigh-performance liquid chromatography. cGas chromatography.
(10−90%) were prepared in the 100 mL jacketed glass flask by adding an excessive 3-nitrobenzonitrile to it containing a known volume of the mixed solvents (about 60 mL). Then, the mixtures were constantly stirred at temperatures 278.15, 283.15, 288.15, 293.15, 298.15, 303.15, 308.15, 313.15, and 318.15 K under atmospheric pressure by using a Teflon-coated magnetic stirrer at a speed of about 200 rpm for at least 13 h. The equilibration time was chosen according to previous studies.18 Once the solution arrived at equilibration, the magnetic stirring was stopped to allow any solid to be precipitated from the solution. Three samples were withdrawn carefully from the upper parts of the solution by using 2 mL of a precooled or preheated syringe attached with a filter (PTFE 0.2 μm), and transferred immediately to a preweighed volumetric flask. Then the sample was diluted using methanol, and 1 μL of liquid was taken out for high-performance liquid chromatography (HPLC) analysis. Analysis Method. The concentration of 3-nitrobenzonitrile was tested by the Agilent-1260 HPLC. The chromatographic column used was a reverse phase column having a type of unimicro Kromasil C18, 5 μm (250 mm × 4.6 mm), and the temperature of which was maintained at about 303 K. The wavelength of the UV detector was 218 nm.18 The methanol + water mixture was employed as mobile phase at the flow rate of 0.8 mL·min−1. Each test was made three times, and the average value of three tests was regarded as the final value of the analysis. The relative standard uncertainty of the determination was estimated to be no greater than 0.026 in mole-fraction solubility. The equilibrium mole-fraction solubility of 3-nitrobenzonitrile (xw,t) in the four binary mixed solvents are attained using eq 1, and the initial contents of the mixed solvents (w) are acquired using eqs 2 and 3.
the aim of this work was to report the solubility of 3-nitrobenzonitrile in solvent mixtures of (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol). In the following, the inverse Kirkwood-Buff integrals (IKBI) method19,20 is used to assess the preferential solvation of 3-nitrobenzonitrile in these binary mixtures analyzed.
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EXPERIMENTAL SECTION Materials and Apparatus. 3-Nitrobenzonitrile employed as solute in the experiment was provided by Shangdong Shuojiao Chemical Co., Ltd., China (0.970 purity in mass fraction). It was recrystallized several times in ethanol. The final 3-nitrobenzonitrile used in solubility measurement was 0.996 purity in mass fraction confirmed with a high-performance liquid chromatography (HPLC, Agilent-1260). The five solvents (ethanol, methanol, n-propanol, ethyl acetate, and isopropyl alcohol) used were analytical grade and were not purified prior to use. The purities of the above solvents were all greater than 0.993 in mass fraction, which were tested using gas chromatography {GC Smart (GC2018)}. The detailed description of these substances was presented in Table 1. The apparatus for solubility determination given in Figure S2 consisted of a 100 mL jacketed glass vessel, a magnetic stirrer, and a circulating (water + isopropyl alcohol) system. The temperature of circulating liquor was controlled through a thermostatic bath (model QYHX-1030) with a standard uncertainty of 0.05 K, which was provide by Shanghai Joyn Electronic Co., Ltd., China. The space between the inner and outer walls of the flask was filled by circulating solutions. Nevertheless, the real temperature measurement was made by a mercury glass microthermometer with a standard uncertainty of 0.02 K that was inserted in the solution. Prior to experiment, the reliability of the apparatus was verified through determining the solubility of benzoic acid in toluene.21,22 Measurement of 3-Nitrobenzonitrile Solubility. The mixed solvents were prepared with an analytical balance (model BSA224S) having a standard uncertainty of 0.0001 g, which was purchased from Satorius Scientific Instrument (Beijing). The solvent mixtures added into the glass vessel was approximately 60 mL. The composition of ethyl acetate in the binary mixed solvents was in the range from 0.1 to 0.9 in mass fraction. The local atmospheric pressure was about 101.1 kPa during the determination process. The solubility determination of 3-nitrobenzonitrile in binary mixed solvents of (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol) was performed by the isothermal dissolution equilibrium method.18,21,22 The saturated mixtures of 3-nitrobenzonitrile in each mass percentage of the solvent ethyl acetate
x w,T =
m1/M1 m1/M1 + m2 /M 2 + m3 /M3
w1 = w =
w2 =
m2 m 2 + m3
m3 m 2 + m3
(1)
(2)
(3)
here m1 denotes the mass of 3-nitrobenzonitrile; m2 denotes the mass of ethyl acetate; and m3denotes the mass of methanol, ethanol, n-propanol, or isopropyl alcohol. M1, M2, and M3 are the molar mass. X-ray Powder Diffraction. So as to show the existence of the polymorph transformation or solvate formation of 3-nitrobenzonitrile during the experiment, the equilibrium solid was collected and tested by the powder X-ray diffraction (XRD). It was carried out to identify the crystal form employed in the work. The XRD patterns were acquired by HaoYuan DX-2700B B
DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 2. Experimental Mole Fraction Solubility (xeT,w × 102) of 3-Nitrobenzonitrile in Mixed Solvent of Ethyl Acetate (w) + Methanol (1 − w) with Various Mass Fractions within the Temperature Range from T/K = (278.15 to 318.15) under p = 101.1 kPa.a w b
T/K
0
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1b
278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15
0.4100 0.5010 0.6219 0.7598 0.9258 1.116 1.341 1.621 1.949
0.4964 0.6165 0.7611 0.9310 1.124 1.379 1.670 2.004 2.417
0.6297 0.7819 0.9541 1.174 1.435 1.750 2.126 2.572 3.097
0.8317 1.024 1.273 1.563 1.907 2.332 2.827 3.425 4.133
1.108 1.373 1.704 2.107 2.576 3.148 3.836 4.650 5.628
1.487 1.852 2.295 2.832 3.480 4.257 5.188 6.297 7.616
1.919 2.394 2.974 3.676 4.524 5.544 6.766 8.225 9.961
2.402 3.006 3.743 4.639 5.723 7.029 8.596 10.47 12.71
2.877 3.613 4.514 5.612 6.945 8.555 10.49 12.81 15.59
3.289 4.149 5.205 6.498 8.071 9.978 12.28 15.05 18.36
3.528 4.400 5.652 7.055 8.758 10.86 13.47 16.61 20.27
a
Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa; relative standard uncertainty ur is ur(x) = 0.026. 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 ethyl acetate in mixed solvents of ethyl acetate + methanol. bTaken from ref 18.
Table 3. Experimental Mole Fraction Solubility (xeT,w × 102) of 3-Nitrobenzonitrile in Mixed Solvent of Ethyl Acetate (w) + Ethanol (1 − w) with Various Mass Fractions within the Temperature Range from T/K = (278.15 to 318.15) under p = 101.1 kPaa w T/K
0b
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.6998
0.8000
0.9000
1b
278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15
0.3116 0.3804 0.4734 0.5820 0.7146 0.8726 1.061 1.304 1.587
0.4552 0.5615 0.6912 0.8492 1.041 1.274 1.557 1.899 2.311
0.6420 0.7927 0.9765 1.200 1.472 1.801 2.200 2.680 3.260
0.8856 1.095 1.350 1.661 2.038 2.495 3.046 3.711 4.510
1.202 1.489 1.839 2.264 2.780 3.405 4.158 5.065 6.153
1.606 1.994 2.466 3.040 3.737 4.579 5.594 6.815 8.278
2.102 2.615 3.241 4.003 4.926 6.042 7.386 9.002 10.94
2.666 3.327 4.133 5.116 6.307 7.748 9.483 11.57 14.06
3.213 4.024 5.017 6.228 7.699 9.478 11.62 14.20 17.29
3.348 4.252 5.370 6.877 8.538 10.55 12.98 15.91 19.42
3.528 4.400 5.652 7.055 8.758 10.86 13.47 16.61 20.27
a
Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa; relative standard uncertainty ur is ur (x) = 0.026. 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 ethyl acetate in mixed solvents of ethyl acetate + ethanol. bTaken from ref 18.
(ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol). The largest solubility of 3-nitrobenzonitrile is observed in neat ethyl acetate. Solubility Correlation and Calculation. Many solubility models are employed in previous works17,21,23 to correlate the solubility of a solid in solvent mixtures. Here three solubility models are applied to correlate the 3-nitrobenzonitrile solubility in solvent mixtures of (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol) at various temperatures, which are the Jouyban− Acree model,17,21,23 a combination of the Jouyban−Acree model with van’t Hoff equation,21,23 and a combination of the Jouyban− Acree model with the Apelblat equation.21,23 The Jouyban−Acree model expressed as eq 4 provides precise mathematical expression for the solute solubility dependence on both temperature and solvent composition for solvent mixtures.17,21,23
(HaoYuan, China) at room temperature and by using Cu Ka radiation of wavelength λ = 1.5405 nm at a tube current of 40 mA and a tube voltage of 40 kV. The tests were performed over a diffraction-angle (2θ) range from 5° to 80° at a step size of 0.01° at a scanning speed of 0.1s/step under atmospheric pressure.
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RESULTS AND DISCUSSION X-ray Powder Diffraction Analysis. The determined patterns of the raw material 3-nitrobenzonitrile and the solid equilibrating with liquid in mixed solvents are given in Figure S3 of the Supporting Information. As can be seen, all XRD patterns of solid in equilibrium with its liquid have the same characteristic peaks with the 3-nitrobenzonitrile (raw material). So, no solvate formation or polymorph transformation is observed during the whole experiment. Solubility Data. The measured 3-nitrobenzonitrile solubility in the four solvent mixtures of (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol) are tabulated in Tables 2−5, respectively, together with that in neat solvents ethyl acetate, methanol, ethanol, n-propanol, and isopropyl alcohol.18 In addition, the solubility dependence on temperature and solvent composition is given in Figures 1−4. As can be shown from Tables 2−5 that the 3-nitrobenzonitrile solubility is a function of solvent composition and temperature. It increases with a rise temperature and mass fraction of ethyl acetate for the solvent mixtures of
ln x w,T = w1 ln x1,T + w2 ln x 2,T +
w1w2 T /K
2
∑ Ji (w1 − w2)i i=0
(4)
here xw,T signifies the solubility of 3-nitrobenzonitrile in mole fraction in mixtures at temperature T/K; w1 and w2 denote the mass fraction composition of solvents 1 (ethyl acetate) and C
DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Table 4. Experimental Mole Fraction Solubility (xeT,w × 102) of 3-Nitrobenzonitrile in Mixed Solvent of Ethyl Acetate (w) + n-propanol (1 − w) with Various Mass Fractions within the Temperature Range from T/K = (278.15 to 318.15) under p = 101.1 kPa w T/K
0b
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1b
278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15
0.2497 0.3077 0.3803 0.4749 0.5917 0.7295 0.8974 1.111 1.351
0.4309 0.5364 0.6658 0.8242 1.017 1.252 1.538 1.883 2.300
0.6694 0.8321 1.031 1.274 1.569 1.928 2.361 2.884 3.514
0.9574 1.190 1.474 1.820 2.240 2.749 3.363 4.104 4.993
1.295 1.611 1.996 2.466 3.035 3.724 4.556 5.556 6.755
1.687 2.101 2.608 3.224 3.972 4.876 5.967 7.277 8.848
2.123 2.650 3.295 4.081 5.034 6.187 7.577 9.248 11.25
2.583 3.233 4.030 5.001 6.181 7.609 9.330 11.40 13.88
3.034 3.811 4.764 5.928 7.344 9.060 11.13 13.62 16.60
3.408 4.299 5.394 6.735 8.37 10.35 12.75 15.64 19.10
3.528 4.400 5.652 7.055 8.758 10.86 13.47 16.61 20.27
a
Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa; relative standard uncertainty ur is ur (x) = 0.026. 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 ethyl acetate in mixed solvents of ethyl acetate + n-propanol. bTaken from ref 18.
Table 5. Experimental Mole Fraction Solubility (xeT,w × 102) of 3-Nitrobenzonitrile in Mixed Solvent of Ethyl Acetate (w) + Isopropyl Alcohol (1 − w) with Various Mass Fractions within the Temperature Range from T/K = (278.15 to 318.15) under p = 101.1 kPaa w b
T/K
0
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
0.9000
1b
278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15
0.1696 0.2155 0.2741 0.3499 0.4462 0.5649 0.7109 0.9054 1.143
0.3011 0.3816 0.4831 0.6107 0.7711 0.9721 1.224 1.539 1.931
0.5007 0.6321 0.7966 1.002 1.259 1.579 1.977 2.471 3.083
0.7796 0.9813 1.233 1.545 1.934 2.415 3.010 3.744 4.648
1.136 1.427 1.789 2.238 2.792 3.475 4.315 5.348 6.612
1.553 1.950 2.442 3.049 3.797 4.716 5.842 7.217 8.894
2.007 2.521 3.157 3.939 4.900 6.077 7.515 9.264 11.39
2.466 3.102 3.887 4.852 6.035 7.479 9.239 11.37 13.96
2.899 3.654 4.585 5.729 7.129 8.836 10.91 13.42 16.45
3.280 4.145 5.213 6.524 8.128 10.08 12.45 15.31 18.76
3.528 4.400 5.652 7.055 8.758 10.86 13.47 16.61 20.27
a
Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.45 kPa; Relative standard uncertainty ur is ur (x) = 0.026. 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 ethyl acetate in mixed solvents of ethyl acetate + isopropyl alcohol. bTaken from ref 18.
⎡ ⎤ B1 ln x w,T = w1⎢A1 + + C1 ln(T /K)⎥ ⎣ ⎦ T /K ⎡⎛ ⎤ B2 + w2⎢⎜A 2 + + C2 ln(T /K)⎥ ⎦ ⎢⎣⎝ T /K
2 (methanol, ethanol, n-propanol, and isopropyl alcohol) free of solute (3-nitrobenzonitrile), respectively; x1,T and x2,T denote the 3-nitrobenzonitrile solubility in mole fraction in pure solvent; and Ji are the equation parameters in the Jouyban−Acree model. The van’t Hoff−Jouyban−Acree model is the combination of van’t Hoff equation and Jouyban−Acree model. It is expressed as21,23 ln x w,T
+
⎛ ⎛ B1 ⎞ B2 ⎞ ⎟ + w2⎜A 2 + ⎟ = w1⎜A1 + ⎝ ⎝ T /K ⎠ T /K ⎠ +
w1w2 T /K
i=0
F=
(5)
B + C ln(T /K) T /K
i=0
e c − ln x w,T )2 ∑ (ln x w,T i=1
The Apelblat equation has been widely used in describing the solid solubility (ln xT) in solvents and reciprocal of temperature (1/T). ln x T = A +
2
∑ Ji (w1 − w2)i
(7)
The determined solubility of 3-nitrobenzonitrile in the four mixtures is correlated with eqs 4, 5, and 7 with the Mathcad software. The objective function is defined as
2
∑ Ji (w1 − w2)i
w1w2 T /K
(8)
In addition, the root-mean-square deviation (RMSD) and the relative average deviation (RAD) are also employed to evaluate the selected models. N
(6)
RMSD =
here A, B, and C are adjustable parameters; xT is the mole fraction solubility of 3-nitrobenzonitrile in the solvent mixtures at temperature T/K. By combining eq 6 and eq 4, the Apelblat−Jouyban−Acree model is acquired as eq 7.21,23
RAD = D
1 N
c e ∑i = 1 (x w,T )2 − x w,T
N c e ⎛ |x w,T − x w,T |⎞ ⎟⎟ ⎜ ∑⎜ e x w,T ⎠ ⎝
(9)
(10) DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 1. Mole fraction solubility (x) of 3-nitrobenzonitrile in ethyl acetate (w) + methanol (1 − w) mixed solutions with various mass fractions at different temperatures: w, mass fraction of ethyl acetate; ×, w = 1;18 ☆, w = 0.9000; ★, w = 0.8000; ◇ w = 0.7000; △, w = 0.6000; ○, w = 0.5000; □, w = 0.4000; ◆ w = 0.3000; ▲, w = 0.2000; ●, w = 0.1000; ■, w = 0;18 , calculated curves by the Jouyban−Acree model.
Figure 4. Mole fraction solubility (x) of 3-nitrobenzonitrile in ethyl acetate (w) + isopropyl alcohol (1 − w) mixed solutions with various mass fractions at different temperatures: w, mass fraction of ethyl acetate; ×, w = 1;18 ☆, w = 0.9000; ★, w = 0.8000; ◇, w = 0.7000; △, w = 0.6000; ○, w = 0.5000; □, w = 0.4000; ◆, w = 0.3000; ▲, w = 0.2000; ●, w = 0.1000; ■, w = 0;18 , calculated curves by the Jouyban−Acree model.
On the basis of the 3-nitrobenzonitrile solubility determined in this work, the model parameters in eqs 4, 5, and 7 are acquired and presented in Table S1, along with the obtained values of RAD and the RMSD. The solubility of 3-nitrobenzonitrile in the four mixtures of (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol) are calculated in terms of the obtained parameters’ values. The calculated values with the Jouyban− Acree model are shown graphically in Figures 1−4. Table S1 illustrates that for the four solvent mixtures, the largest value of RAD between the experimental and calculated values is 1.57%, which is obtained with the van’t Hoff−Jouyban−Acree model for the (ethyl acetate + isopropyl alcohol) mixture. In addition, the RMSD values are no greater than 1.152 × 10−3. The values of RAD and RMSD acquired are smaller with the Jouyban−Acree model than with the other two models. In general, the three models may be used to fit the solubility of 3-nitrobenzonitrile in (ethyl acetate + methanol), (ethyl acetate + ethanol), (ethyl acetate + n-propanol), and (ethyl acetate + isopropyl alcohol) mixtures at all initial composition ranges. Preferential Solvation of 3-Nitrobenzonitrile. The IKBI method is valuable for calculating the preferential solvation of nonelectrolyte in mixed solvents, which describes the local solvent composition around the solute in comparison with the global solutions composition.19,20,24−26 The dealing relies upon the value of standard molar Gibbs energies of transfer of solute from pure alcohol to the ethyl acetate (1) + alcohol (2) mixtures and the excess molar Gibbs energy of mixing for the mixed solvents. As has been shown in the publications,19,20,24−26 the studies on preferential solvation can present valuable information relating to the molecular interactions. The preferential solvation parameter of 3-nitrobenzonitrile (compound 3) by the ethyl acetate (compound 1) in ethyl acetate (1) + methanol (ethanol, n-propanol, and isopropyl alcohol) (2) mixtures is described as19,20,24−26
Figure 2. Mole fraction solubility (x) of 3-nitrobenzonitrile in ethyl acetate (w) + ethanol (1 − w) mixed solutions with various mass fractions at different temperatures: w, mass fraction of ethyl acetate; ×, w = 1;18 ☆, w = 0.9000; ★, w = 0.8000; ◇, w = 0.7000; △, w = 0.6000; ○, w = 0.5000; □, w = 0.4000; ◆, w = 0.3000; ▲, w = 0.2000; ●, w = 0.1000; ■, w = 0;18 , calculated curves by the Jouyban−Acree model.
Figure 3. Mole fraction solubility (x) of 3-nitrobenzonitrile in ethyl acetate (w) + n-propanol (1 − w) mixed solutions with various mass fractions at different temperatures: w, mass fraction of ethyl acetate; ×, w = 1;18 ☆, w = 0.9000; ★, w = 0.8000; ◇, w = 0.7000; △, w = 0.6000; ○, w = 0.5000; □, w = 0.4000; ◆, w = 0.3000; ▲, w = 0.2000; ●, w = 0.1000; ■, w = 0;18 , calculated curves by the Jouyban−Acree model.
L δx1,3 = x1,3 − x1 = −δx 2,3
(11)
xL1,3
where denotes the local mole fraction of ethyl acetate (1) in the environment near to 3-nitrobenzonitrile (3) (solvation sphere) and x1 is the mole fraction of ethyl acetate (1) in the bulk solution. The parameter δx1,3 > 0 denotes the excess or deficiency of ethyl acetate of the ethyl acetate (1) + methanol (ethanol,
where N signifies the number of determined data points. xew,T is the measured solubility in the present work, and xcw,T is the calculated solubility using the corresponding model. E
DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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n-propanol, and isopropyl alcohol) (2) mixture in the local region. Such that the 3-nitrobenzonitrile is preferentially solvated by ethyl acetate, when δx1,3 > 0, in the case δx1,3 being < 0, the 3-nitrobenzonitrile is said to be preferentially solvated by methanol (ethanol, n-propanol, or isopropyl alcohol) (2). Nevertheless, if xL1,3 ≈ 1, then complete solvation of the solute is carried out by the ethyl acetate. The parameter δx1,3 in the solvent mixtures may be attained from the inverse Kirkwood−Buff integrals (IKBI) for each solvent component as shown in the following equations.19,20,24−26 δx1,3 =
r3 =
G2,3
(12)
(13)
x VD = RTκT − V3 + 1 1 Q
(14)
0 −x1/ t1 Δtr G3,2 + A 2 e−x1/ t2 → 1 + 2 = A 0 + A1 e
(15)
here κT denotes the isothermal compressibility of the binary mixtures (in GPa−1). Because of the dependence of κT upon solvent composition, the κT dependence on composition of a solvent mixture may be approximately obtained from individual isothermal compressibility of a component as19,20,24−26 κT =
+
(16)
∂x1
⎡ ∂ 2G Exc ⎤ 1+2 ⎥ Q = RT + x1x 2⎢ 2 ⎣ ∂x 2 ⎦T , p
dV dx1
(22)
V2 = V − x1
dV d x1
(23)
3 G1Exc + 2 = − 0.402 + 2.966 × 10 (1 − x1)
− 3.947 × 103(1 − x1)2 + 1.652 × 103(1 − x1)3 − 674.32(1 − x1)4
(24)
3 G1Exc + 2 = − 3.849 + 2.560 × 10 (1 − x1)
− 2.318 × 103(1 − x1)2 − 576.79(1 − x1)3
o ⎞ ⎛ ∂Δtr G(3,2 → 1 + 2)
⎟ ⎠T , P
V1 = V + x 2
here V is the molar volume of the binary mixtures studied and calculated as V = (x1M1 + x2M2)/ρ. The value of M1 is 32.04 g· mol−1 for methanol, 46.07 g·mol−1 for ethanol, 60.06 g·mol−1 for n-propanol and isopropyl alcohol, and M2 is 88.1 g·mol−1 for ethyl acetate. The densities of these binary mixtures studied have been collected from the literature.28−30 −1 The G1Exc + 2 (J·mol ) values at all the temperatures considered should be needed with the intention of calculating the Q values. They are computed at 328.15 K for ethyl acetate (1) + alcohol (2) binary mixtures with eq 24 for methanol, eq 25 for ethanol, eq 26 for isopropyl alcohol, and eq 27 for n-propanol. The values of G1Exc+ 2 (J·mol−1) at other temperatures are evaluated with eq 28, here H1Exc + 2 denotes the excess molar enthalpy of the binary mixtures, T1 is 328.15 K, and T2 is one of the other temperatures under study.20 The function H1Exc+ 2 for the four binary mixtures is described as eqs 29, 30, 31, and 32 for methanol, ethanol, isopropyl alcohol, and n-propanol, respectively.24,25
here xi is the mole fraction of component i in the solution and κoT,i is the isothermal compressibility of the neat solvent i with the values 1.252 GPa−1 for methanol, 1.153 GPa−1 for ethanol, 1.025 GPa−1 for n-propanol, 0.523 GPa−1 for isopropyl alcohol, and 1.207 GPa−1 for ethyl acetate at 298.15 K.27 In eqs 13, 14, and 15, V̅ 1 and V̅ 2 denote the partial molar volumes of the solvents in the binary mixture (cm3·mol−1). The parameter D (eq 17) represents the derivative of standard molar Gibbs energy of transfer of 3-nitrobenzonitrile from pure alcohol (2) to ethyl acetate (1) + alcohol (2) solutions with respect to ethyl acetate composition (in kJ·mol−1). The parameter Q (eq 18) involves the second derivative of the excess molar Gibbs energy of mixing of the two solvents (G1Exc + 2) with respect to the alcohol composition in the binary mixtures (kJ·mol−1).19,20,24−26 Vcor denotes the correlation volume, and r3 is the molecular radius of 3-nitrobenzonitrile computed with eq 19 using NAv as the Avogadro’s number. Because of no partial molar volume of 3-nitrobenzonitrile (3) in the mixtures reported in the previous publications, here it is considered similar to that for pure 3-nitrobenzonitrile.20,24−26 In this manner, the partial molar volume of 3-nitrobenzonitrile (V̅ 3) in these solvent mixtures (cm3·mol−1) is obtained from the molar mass (148.12 g·mol−1) and density (1.310 g·cm−3)18 as 113.1 cm3·mol−1. From this molar volume, 3-nitrobenzonitrile radius value (r3) is computed with eq 19 as 0.355 nm. D=⎜ ⎝
(21)
Thus, the D values are calculated from the first derivative of eq 21 solved in terms of ethyl acetate composition varying by 0.05 in mole fraction. The attained D values are tabulated in Table S5. The partial molar volumes of alcohols and ethyl acetate in the binary mixtures are computed on the basis of the following expressions:
L L Vcor = 2522.5[r3 + 0.1363(x1,3 V1̅ + x 2,3 V2)1/3 − 0.085]3
o x 2κT,2
(20)
0 The variations of ΔtrG3,2→1 + 2 with ethyl acetate composition at different temperatures are shown in Figure S4 and correlated with eq 21. The attained equation coefficients are presented in Table S4.
x 2 V2D Q
o x1κT,1
(19)
⎛ x3,2 ⎞ 0 ⎟⎟ Δtr G3,2 ⎜ → 1 + 2 = RT ln⎜ ⎝ x3,1 + 2 ⎠
with G1,3 = RTκT − V3 +
3 × 1021V3̅ 4πNAV
By using the mole fraction solubility data of 3-nitrobenzonitrile (Tables 2−5), the numerical values of standard molar Gibbs energies of transfer of 3-nitrobenzonitrile from pure alcohol (2) to ethyl acetate (1) + alcohol (2) mixtures can be obtained using eq 20 at different temperatures and are presented in Tables S2 and S3.
x1x 2(G1,3 − G2,3) x1G1,3 + x 2G2,3 + Vcor
3
+ 334.20(1 − x1)4 (17)
(25)
3 G1Exc + 2 = 0.917 + 1.959 × 10 (1 − x1)
− 1.379 × 103(1 − x1)2 − 1.790 × 103(1 − x1)3 + 1.199 × 103(1 − x1)4
(18) F
(26) DOI: 10.1021/acs.jced.8b00230 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
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Figure 5. δx1,3 values of 3-nitrobenzonitrile (3) from methanol, ethanol, n-propanol, and isopropyl alcohol (2) to ethyl acetate (1) + methanol (2), ethyl acetate (1) + ethanol (2), ethyl acetate (1) + n-propanol (2), and ethyl acetate (1) + isopropyl alcohol (2) mixtures at several temperatures. (a) Ethyl acetate (1) + methanol (2); (b) ethyl acetate (1) + ethanol (2); (c) ethyl acetate (1) + n-propanol (2); (d) ethyl acetate (1) + isopropyl alcohol (2).
values of these parameters (Kirkwood−Buff integrals) show that 3-nitrobenzonitrile exhibits affinity for both solvents in ethyl acetate (1) + alcohol (2) binary mixtures. The correlation volumes are iterated by using eqs 11, 12, and 15 to acquire an almost nonvariant value of the Vcor. The iterated values of Vcor and δx1,3 in the solvent systems and different temperatures under consideration are reported in Tables S10−S13. Moreover, the variation of the δx1,3 values versus different compositions of ethyl acetate in binary mixture is shown in Figure 5. As can be seen in Figure 5, the δx1,3 values change nonlinearly with ethyl acetate (1) composition in the binary mixtures. The addition of ethyl acetate to alcoholic solution of 3-nitrobenzonitrile causes the δx1,3 values to be negative from the pure alcohol up to the mixture with composition x1 = 0.30 (293.15 K, 298.15, and 303.15 K) and x1 = 0.25 (308.15 K, 313.15 K) for ethyl acetate (1) + methanol (2) mixture, x1 = 0.371 for ethyl acetate (1) + ethanol (2) mixture, x1 = 0.433 for ethyl acetate (1) + n-propanol (2) mixture, and x1 = 0.45 (293.15 K) and x1 = 0.216 (298.15 K, 303.15 K, 308.15 K, 313.15 K) for ethyl acetate (1) + isopropyl alcohol (2) mixture. The minimum negative values of δx1,3 are obtained in the mixture x1 = 0.10 for ethyl acetate (1) + methanol (2) mixture, x1 = 0.15 for ethyl acetate (1) + ethanol (2) and ethyl acetate (1) + n-propanol (2) mixtures, and x1 = 0.10−0.15 for ethyl acetate (1) + isopropyl alcohol (2), respectively. This case shows that the local mole fractions of alcohol are higher than those of the mixtures and consequently the values of δx1,3 are negative, which indicates that alcohol is preferred over the ethyl acetate in the solvation shell. This is possibly explicated by the ordered structure of alcohol molecules around the apolar group of 3-nitrobenzonitrile (aromatic rings, Figure S1) in the alcohol-rich solutions, which is formed via hydrophobic hydration in alcohol-rich solutions.24−26
−3 G1Exc + 2.099(1 − x1) + 2 = − 8.605 × 10
− 0.329(1 − x1)2 − 3.681(1 − x1)3 + 1.926(1 − x1)4 Exc G1Exc + 2(T2) = G1 + 2(T1) − T
(27)
∫T
T2
1
≈
⎛1⎞ ⎜ ⎟ H1Exc + 2 d⎝ ⎠ T
⎛ T2 Exc T2 ⎞ G1 + 2(T1) + H1Exc ⎟ + 2 ⎜1 − T1 T1 ⎠ ⎝
(28)
3 H1Exc + 2 = 16.437 + 5.055 × 10 (1 − x1)
− 7.148 × 103(1 − x1)2 + 2.330 × 103(1 − x1)3 − 252.34(1 − x1)4
(29)
3 H1Exc + 2 = 18.328 + 6.826 × 10 (1 − x1)
− 1.270 × 104(1 − x1)2 + 1.032 × 104(1 − x1)3 − 4.465 × 103(1 − x1)4
(30)
3 H1Exc + 2 = − 9.395 + 8.678 × 10 (1 − x1)
− 1.386 × 104(1 − x1)2 + 9.099 × 103(1 − x1)3 − 3.902 × 103(1 − x1)4
(31)
−3 H1Exc + 7.71(1 − x1) − 11.428(1 − x1)2 + 2 = 1.368 × 10
+ 5.749(1 − x1)3 − 2.012(1 − x1)4
(32)
The computed G1,3 and G2,3 values for 3-nitrobenzonitrile in all solvent compositions are listed in Tables S6−S9. The negative G
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ethyl acetate (1) + (methanol, ethanol, n-propanol, and isopropyl alcohol) (2) mixtures (0−100% by w/w) increased when amount of the ethyl acetate and also the temperature increased. The dependence of 3-nitrobenzonitrile solubility upon temperature and mass fraction of ethyl acetate was correlated using the Jouyban−Acree model, van’t Hoff−Jouyban−Acree model and Apelblat−Jouyban−Acree model. The values of RAD and RMSD were all less than 1.57% and 11.52 × 10−4, respectively. Furthermore, quantitative values relating to the local mole fraction of ethyl acetate around 3-nitrobenzonitrile were obtained in terms of the IKBI method. 3-Nitrobenzonitrile is preferentially solvated by alcohol in alcohol-rich mixtures while it is preferentially solvated by ethyl acetate in mixtures with intermediate and rich composition of ethyl acetate. This case may be due to the existence of interactions between the solute and solvent system such as the hydrophobic hydration.
However, in the mixtures of ethyl acetate (1) + methanol (2) with composition 0.25 (0.30) < x1 < 1, ethyl acetate (1) + ethanol (2) with composition 0.371 < x1 < 1, ethyl acetate (1) + n-propanol (2) with composition 0.433 < x1 < 1, and ethyl acetate (1) + isopropyl alcohol (2) with composition 0.45 (0.216) < x1 < 1, the values of δx1,3 are positive, which indicates that the local mole fractions of ethyl acetate are greater than that of the mixtures, and therefore, 3-nitrobenzonitrile is preferentially solvated by ethyl acetate. The ethyl acetate is preferred over the alcohol in the solvation shell. This behavior probably can be related to the breaking of the same ordered structure of alcohol around the apolar moieties of 3-nitrobenzonitrile.24,25 The δx1,3 exhibits maximum value in x1 = 0.55 with δx1,3 = (2.070 to 2.446) × 10−2 for ethyl acetate (1) + methanol (2) mixture, x1 = 0.60 with δx1,3 = (1.902 to 2.056) × 10−2 for ethyl acetate (1) + ethanol (2) mixture, and x1 = 0.55− 0.65 with δx1,3 = (1.795 to 8.438) × 10−2 for ethyl acetate (1) + isopropyl alcohol (2) mixture. However, for ethyl acetate (1) + n-propanol (2) mixture with composition x1 = 0.433 to 1, the δx1,3 values are all lower than 1.0 × 10−2. Consequently they are just qualitative due to uncertainties propagation effects rather than preferential solvation.31,32 As can also be seen from Figure 5 that in the regions with intermediate composition, the preferential solvation magnitude of 3-nitrobenzonitrile by ethyl acetate is higher in ethyl acetate (1) + isopropyl alcohol (2) binary mixtures than in the other solvent mixtures at 298.15, 308.15, and 313.15 K. From Figure 5, it is noteworthy that the influence of temperature on preferential solvation in intermediate compositions to ethyl acetate-rich regions is relatively small for the ethyl acetate (1) + methanol (2) and ethyl acetate (1) + ethanol (2) mixtures; while for the ethyl acetate (1) + isopropyl alcohol (2) mixture, the temperature has a large effect on the δx1,3 values, especially at 298.15, 308.15, and 313.15 K. According to a functional group and structural analysis, 3-nitrobenzonitrile can act as a Lewis base due to lone electron pairs on the oxygen atom of the −NO2 group and nitrogen atom of − CN group, to interact with hydrogen atoms in a protic solvent (methanol, ethanol, n-propanol, and isopropyl alcohol). On the basis of the preferential solvation analysis, it is conjecturable that in the region of 0 < x1 < 0.25 (0.30) for the ethyl acetate (1) + methanol (2) mixture, 0 < x1 < 0.371 for the ethyl acetate (1) + ethanol (2) mixture, and 0 < x1 < 0.45 (0.216) for the ethyl acetate (1) + isopropyl alcohol (2) mixture, where 3-nitrobenzonitrile is preferentially solvated by alcohol, the solute could be acting mainly as a Lewis base in the presence of alcohol because the Kamlet−Abboud−Taft (KAT) acidity parameters are α = 0 for ethyl acetate, 0.990 for methanol, 0.850 for ethanol, 0.84 for n-propanol, and 0.687 for isopropyl alcohol, respectively.27,33 Contrary to other compounds,24−26 3-nitrobenzonitrile molecule has apparently no possible Lewis acid behavior because no acidic hydrogen atom is present (Figure S1). For this case, it is very difficult to find a justification for the positive δx1,3 values in those binary mixtures with intermediate and ethyl acetate-rich composition. For other compounds with hydrogen-donation ability, this tendency has been explained based on the Lewis acidic behavior with the solvent (1) molecules because these solvents are usually more basic than the ethyl acetate molecule as described by the KAT hydrogen bonding acceptor parameters β, that is, β = 0.66 for methanol, β = 0.75 for ethanol, β = 0.90 for n-propanol, β = 0.84 for isopropyl alcohol, and β = 0.45 for ethyl acetate.27,34
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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.8b00230. Figures: chemical structure of 3-nitrobenzonitrile; experimental apparatus; XRD patterns; Gibbs energy of transfer. Tables: parameters of equations; Gibbs energy of transfer; coefficients of equations; D, G1,3, G2,3, and δx1,3 values; correlation volume and values (PDF)
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AUTHOR INFORMATION
Corresponding Author
* Tel: + 86 514 87975568. Fax: + 86 514 87975244. E-mail:
[email protected]. ORCID
Renjie Xu: 0000-0003-1888-8864 Hongkun Zhao: 0000-0001-5972-8352 Funding
This work was supported by the Science and Technology Research Key Project of the Education Department of Jiangsu Province (Project No. SJCX17_0621) and the Practice Innovation Project of Jiangsu Province for Post Graduate Students (Project No. XKYCX17_039). Notes
The authors declare no competing financial interest.
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REFERENCES
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CONCLUSION From the results acquired in this work, it was observed that the equilibrium solubility of the 3-nitrobenzonitrile in H
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