Study on the Solubilities of Mononitro-Substituted Products of Nitration

Article pubs.acs.org/jced

Study on the Solubilities of Mononitro-Substituted Products of Nitration of m‑Toluic Acid in Several Solvents at Temperatures between 297.65 and 351.75 K Xiaojun He,† Ze Tan,*,† Qinbo Wang,*,‡ and Yinchuan Pei† †

Department of Chemical Engineering, Hunan University, Changsha 410082, Hunan, People’s Republic of China Jiangxi Keyuan Biopharm Co. Ltd, Jiujiang 332700, Jiangxi, People’s Republic of China

‡

ABSTRACT: Mononitro-substituted products derived from the nitration of m-toluic acid are 3-methyl-4-nitrobenzoic acid, 3-methyl-2-nitrobenzoic acid, and 5-methyl-2-nitrobenzoic acid, which are all crucial intermediates of pesticides and medicines. The solubilities of 3-methyl-4-nitrobenzoic acid, 3-methyl-2-nitrobenzoic acid, and 5-methyl-2-nitrobenzoic acid in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid were measured at different temperatures (297.65−351.75 K) and under atmospheric pressure. As expected, the same solute has different solubilities in different solvents, and the dissolved amounts of these three solutes are also diverse in the same solvent. Subsequently the experimental solubility data of three mononitro-substituted products of m-toluic acid nitration in several solvents were correlated with the modified Apelblat equation and the NRTL activity coefficient model, and the calculated values are in excellent agreement with known experimental data in the temperature range studied.

1. INTRODUCTION

It should be noted that in previously reported literatures, the solubilities of 3-M-4-NBA have been measured by Wu in methanol, ethanol, and n-propanol at temperatures between 283.15 and 318.15 K.15,16 Acree also have studied the solubility data of 3-M-4-NBA in methanol and ethanol at 298.2 K.17 In addition, Li18 and Hart19 also have studied 2-methyl-3-nitrobenzoic acid in several solvents. However, there are no available data on the solubilities of 3-M-2-NBA and 5-M-2-NBA in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid although several reports on the solubilities of 3-M-4-NBA have been disclosed. Because 3-M-2-NBA is the major product and 5-M-2-NBA is one of the major side products for m-toluic acid nitration, the lack of their solubility data can severely hinder the development of an efficient separation method via selective crystallization. Therefore, it would be very useful for detailed information on the solubilities of these products to be readily available. In this work, the solubilities of 3-M-2-NBA, 3-M-4-NBA, and 5-M-2-NBA in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid at different temperatures (297.65−351.75 K) and under atmospheric pressure were measured, respectively. Then, the experimental solubility values of these mononitro-substituted products in several solvents were used to correlate with the modified Apelblat equation and the NRTL activity coefficient model, and it was discovered that the calculated values are in excellent agreement with known experimental data in the temperature range studied.

Nitration of m-toluic acid is one of the important reactions in chemical industry, and its mononitro-substituted products, 3-methyl-2-nitrobenzoic acid (3-M-2-NBA), 3-methyl-4-nitrobenzoic acid (3-M-4-NBA), and 5-methyl-2-nitrobenzoic acid (5-M-2-NBA), are crucial intermediates of pesticides and medicines.1−3 3-M-2-NBA can be applied to produce cyantraniliprole,4 and 3-M-4-NBA is mainly utilized to produce an angiotensin-receptor blocker, telmisartan,5 which is widely used as the hypertensive drug, and is the second generation of anthranilamide insecticides developed by E. I. Du Pont Company. On the other hand, 5-M-2-NBA can be used as starting material for the production of raltiterxed,6 which is helpful for the treatment of advanced stage rectum cancer. As such, all three compounds have significant values. The equation of m-toluic acid mononitration is shown below

The common nitrating agents are nitric acid,7−11 urea nitrate,1,2 nitrourea,1,2 guanidine nitrate,2 nitroguanidine,2 and N2O5.3 This reaction needs to be run for a relatively long time at relatively low temperatures. However, the selectivity of the reaction is not very high. All three compounds are produced with 3-M-2-NBA being the major product (∼65%). It would be highly desirable in terms of scientific and engineering values to search for a method that could efficiently separate these three products. Because of their high boiling points and melting points,12−14 crystallization would be the method of choice. © 2017 American Chemical Society

Received: May 13, 2017 Accepted: August 14, 2017 Published: August 29, 2017 3360

DOI: 10.1021/acs.jced.7b00431 J. Chem. Eng. Data 2017, 62, 3360−3367

Journal of Chemical & Engineering Data

Article

Table 1. Suppliers and Mass Fractions of the Chemical Reagents

a

component

suppliers

CAS No.

mass fractions

analysis method

3-methyl-4-nitrobenzoic acid 3-methyl-2-nitrobenzoic acid 5-methyl-2-nitrobenzoic acid methanol ethanol n-propanol formic acid acetic acid propanoic acid water

Aladdin Chemistry Co. Aladdin Chemistry Co. Beijing InnoChem Science & Technology Co., Ltd. Shanghai Titan Scientific Co., Ltd. Xilong Chemical Co., Ltd. Tianjin Fengchuan Chemical Reagent Technologies Co., Ltd. Sinopharm Chemical Reagent Co., Ltd. Sinopharm Chemical Reagent Co., Ltd. Shanghai Shanpu Chemical Reagent Co., Ltd. Hangzhou Wahaha Group Co.

3113-71-1 5437-38-7 3113-72-2 67-56-1 64-17-5 71-23-8 64-18-6 64-19-7 1979-9-4 7732-18-5

>0.990 >0.980 >0.980 >0.995 >0.997 >0.998 >0.980 >0.995 >0.998 >0.999

HPLCa HPLCa HPLCa GCb GCb GCb GCb GCb GC

High-performance liquid chromatography. bGas chromatograph.

2. EXPERIMENTAL SECTION 2.1. Materials. 3-M-2-NBA and 3-M-4-NBA were obtained from Aladdin Chemistry Co., and 5-M-2-NBA was obtained from Beijing InnoChem Science & Technology Co., Ltd. The declared purities of these compounds are all >0.980 in mass and checked by HPLC. Purified water was purchased from the local supermarket (596 mL each bottle), which was produced by Hangzhou Wahaha Group Co., and the resistivity was measured to be 18.2 MΩ cm. Except for the above chemicals, the major information on methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid are all given in Table 1. 2.2. Experimental Procedures. The solubilities of 5-M-2NBA, 3-M-2-NBA and 3-M-4-NBA in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid at different temperatures and under atmospheric pressure were measured by a method introduced by Jiang20 and Chen.21 The main apparatus consists of a (solid + liquid) equilibrium cell (120 mL), a laser-detecting apparatus, a system used for temperature-controlling and measurement, as well as a magnetic stirring machine. In each experiment, all chemicals were carefully weighted and placed in the equilibrium cell by using an electronic analytical balance from Mettler Toledo instrument Co. Ltd. (type AL204, uncertainty of the instrument is 0.0001 g). The cell was heated in a thermostatic water bath and the mixture in the cell was stirred using a magnetic stirrer bar continuously. At first, the temperature of the mixture was elevated in a stepwise fashion at the rate of around 2.5 K/h. Then the temperature was increased at 0.2 K/h or less when the solute was almost completely dissolved; meanwhile, the laser monitoring apparatus was applied to help to find the equilibrium temperature. A steady laser beam was passed through the mixture and it was received by a laser power meter. The working principle is that if there were solid material in the path of the laser beam, the light would be scattered around and the transmitted intensity would be greatly reduced. The intensity of the transmitted laser light is measured and recorded by a computer according to the photovoltage. The relevant temperature at a given composition is determined when the solid phase just disappears. In order to ensure the repeatability, each data point of the experimental solubility was measured at least twice, and the relative uncertainty of each data has to be within 5%. To check the accuracy and reliability of this experimental method used in this study, a comparison for the measured solubility data of 3-M-4-NBA in pure methanol, ethanol, and n-propanol has been carried out against the literature published data in Figures 1−3. In addition, the solubility data of 3-M-4-NBA can be found in Table 2. Figure 1 shows that

Figure 1. Comparison between experimental solubility of 3-M-4-NBA in methanol with the literature data: □, the measured solubility; Δ, literature data from Wu; S is defined as the mass of solute (g) in 100 g solvent.

the measured solubility values of 3-M-4-NBA in methanol are in excellent agreement with literature data reported by Wu,16 which indicates the accuracy of our experimental technique and the reliability of the measured solubility data. From Figures 2 and 3, it can be concluded that the trend of the measured solubilities of 3-M-4-NBA in ethanol and n-propanol are consistent with the literature values. However, in the higher temperature region there are rather significant deviations between the solubilities of 3-M-4-NBA in pure ethanol and n-propanol in this work and those reported by Wu,16 which may be due to the different experimental technique used. In the previous work, the analytical method was used to measure the solubility of 3-M-4-NBA, and the solid−liquid equilibrium was judged by high-performance liquid chromatography; and in the present work, the solubilities of 3-M-4-NBA were determined with the synthetic method20,21 in which laser monitoring was used to measure the equilibrium temperature.

3. RESULTS AND DISCUSSION 3.1. Experimental Data. Values of measured solubilities of 3-M-4-NBA, 3-M-2-NBA, or 5-M-2-NBA in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid at various temperatures are all shown in Tables 2, 3, or 4, where T and S represent the absolute temperature and the mass solubility, respectively. In addition, the measured solubilities of different solutes in the same solvent at different temperatures are also plotted in Figures 4 to 10. It can be clearly found that the solubilities of all solutes increase with increasing temperature from Tables 2 to 4. Table 4 shows that the solubilities of 5-M-2-NBA are different in different solvents, and it increases from water to acids then to alcohols. The same goes for the solubilities of 3-M-4-NBA and 3-M-2-NBA in these solvents from Tables 2 and 3. Meanwhile, Figure 4 shows that the order of the dissolved amount of three solutes in water 3361



Article

Table 2. Solubility Values of 3-M-4-NBA in Different Pure Solvents at Different Temperatures and Pressure p = 101.3 kPaa,b T/K 311.25 317.05 320.65 322.15 325.15

S/(g/100g) 0.0223 0.0276 0.0317 0.0340 0.0380

Sc1/(g/100g) 0.0219 0.0278 0.0322 0.0341 0.0384

RD1/% −1.79 0.72 1.58 0.29 1.05

Sc2/(g/100g) 0.0223 0.0275 0.0318 0.0339 0.0384

297.65 302.45 306.65 310.35 314.15 317.45

5.135 6.029 7.026 7.991 9.017 10.12

5.114 6.067 7.025 7.977 9.070 10.13

−0.40 0.62 −0.01 −0.17 0.59 0.06

5.135 6.057 7.041 7.970 9.077 10.13

299.95 304.75 306.75 310.15 314.65 318.65

4.754 5.412 5.907 6.453 7.531 8.521

4.746 5.486 5.834 6.486 7.484 8.521

−0.18 1.37 −1.24 0.51 −0.62 0.00

4.776 5.462 5.866 6.475 7.493 8.517

308.35 312.75 316.95 320.85 323.95 327.35

4.194 5.024 5.877 6.730 7.612 8.514

4.227 5.000 5.846 6.738 7.527 8.482

0.78 −0.47 −0.53 0.12 −1.11 −0.37

4.249 4.994 5.838 6.717 7.507 8.460

310.85 314.95 318.85 321.95 325.15 329.55

0.8004 0.9664 1.135 1.309 1.481 1.704

0.8093 0.9632 1.132 1.284 1.459 1.733

1.11 −0.33 −0.26 −1.86 −1.47 1.70

0.8282 0.9468 1.145 1.263 1.462 1.739

299.65 308.15 314.45 319.25 323.95 328.55

2.404 3.067 3.785 4.437 5.207 5.959

2.367 3.133 3.826 4.437 5.113 5.856

−1.55 2.17 1.09 0.00 −1.81 −1.73

2.402 3.078 3.788 4.439 5.123 5.905

305.45 314.15 316.75 320.85 324.15 328.85

2.535 3.239 3.580 4.049 4.579 5.175

2.504 3.311 3.591 4.073 4.500 5.174

−1.23 2.21 0.30 0.59 −1.72 −0.01

2.520 3.271 3.548 4.052 4.508 5.194

RD2/%

T/K

Water 0.04 328.05 −0.33 334.05 0.40 337.65 −0.42 343.15 0.93 347.05 Methanol 0.00 320.05 0.46 322.65 0.22 325.25 −0.26 327.45 0.66 329.85 0.10 Ethanol 0.45 321.95 0.93 325.95 −0.68 329.15 0.34 331.95 −0.50 335.15 −0.05 n-Propanol 1.29 330.65 −0.58 333.65 −0.67 336.65 −0.18 339.15 −1.38 341.75 −0.64 Formic Acid 3.47 332.65 −2.03 335.15 0.83 338.85 −3.46 341.95 −1.31 344.95 2.09 Acetic Acid −0.09 333.45 0.37 337.95 0.06 341.85 0.04 344.45 −1.61 348.55 −0.89 Propanoic Acid −0.59 332.45 0.99 336.15 −0.91 340.65 0.07 344.95 −1.55 348.35 0.38

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

RD2/%

0.0436 0.0542 0.0641 0.0753 0.0873

0.0431 0.0542 0.0621 0.0762 0.0878

−1.15 0.00 −3.12 1.20 0.57

0.0432 0.0549 0.0628 0.0763 0.0869

−0.87 1.22 −1.97 1.39 −0.50

11.13 12.07 12.92 14.11 15.06

11.03 12.01 13.06 14.01 15.13

−0.86 −0.56 1.11 −0.69 0.41

11.01 12.01 13.07 14.02 15.15

−1.06 −0.54 1.20 −0.64 0.58

9.514 10.84 12.12 13.39 14.92

9.502 10.86 12.11 13.34 14.91

−0.14 0.23 −0.05 −0.40 −0.07

9.504 10.87 12.12 13.38 14.94

−0.11 0.28 0.01 −0.10 0.12

9.427 10.39 11.54 12.68 13.93

9.506 10.53 11.64 12.64 13.77

0.84 1.36 0.89 −0.28 −1.18

9.482 10.51 11.65 12.66 13.81

0.58 1.22 0.94 −0.19 −0.90

1.914 2.140 2.456 2.759 3.082

1.951 2.143 2.457 2.750 3.062

1.92 0.16 0.04 −0.32 −0.67

1.938 2.137 2.455 2.774 3.094

1.26 −0.13 −0.05 0.55 0.38

6.752 7.622 8.446 9.214 10.25

6.746 7.661 8.538 9.169 10.24

−0.08 0.51 1.09 −0.49 −0.10

6.817 7.735 8.562 9.138 10.13

0.98 1.48 1.38 −0.83 −1.17

5.761 6.429 7.279 8.136 8.948

5.747 6.391 7.257 8.177 8.974

−0.25 −0.59 −0.29 0.51 0.30

5.782 6.450 7.277 8.162 8.895

0.36 0.33 −0.02 0.32 −0.59

Standard uncertainties u are u(T) = 0.05 K, ur(p) = 0.05, ur(S) = 0.05. bRDi = (Sci − S)/S × 100. S is the experimental data, Sc1 and Sc2 represent the Apelblat equation and NRTL model correlated solubility, respectively. RD1 and RD2 represent the relative deviation between the correlated solubility by the Apelblat equation and NRTL model and the experimental data, respectively. The solubility is defined as the mass of solute (g) in 100 g of solvent. a

3.2. Correlation of Experimental Data. Modified Apelblat Correlation. To describe the temperature dependence of the mononitro substituted products’ solubility in above solvents more quantitatively, the solubilities has been fitted by the modified Apelblat equation22,23

(from small to large) is 3-M-4-NBA, 3-M-2-NBA, and 5-M-2NBA and most solvents reflected the same situation. There are some differences between the solubilities of 3-M-4-NBA and 3-M-2-NBA in water and acids; from Figures 4, 8, 9 and 10, it could be seen that they are slightly soluble in water. Figures 5−7 tell that all of these solutes are easy to dissolve in methanol, ethanol, and n-propanol, but 5-methyl-2-nitrobenzoic acid is much easier to dissolve than the other two solutes.

ln x = A + 3362

B + C ln(T ) T DOI: 10.1021/acs.jced.7b00431 J. Chem. Eng. Data 2017, 62, 3360−3367


Article

where x is the molar fraction solubility of the mononitro substituted products; T is the absolute temperature; and A, B, and C are the parameters and are listed in Tables 5 to 7. We used the Nelder−Mead Simplex approach24 as the optimal algorithm applied in the parameter estimation program. As for the Function fminsearch in the optimization toolbox of Matlab (Mathwork, MA), the Nelder−Mead Simplex approach was used to calculate the minimum value of the objective function, which is the relative average deviation (RAD) between the measured solubility data and calculated solubility. The equation is as follows Figure 2. Comparison between experimental solubility of 3-M-4-NBA in ethanol with the literature data: □, the measured solubility; Δ, literature data from Wu; S is defined as the mass of solute (g) in 100 g solvent.

RAD =

1 n

n

⎛ xci − xi ⎞ × 100⎟ ⎝ xi ⎠

∑ abs⎜ i=1

(2)

where n is the total number of experimental points, xci and xi are the calculated and measured solubilities. The correlated values and the corresponding RD are listed in Tables 2 to 4. Meanwhile, in Tables 5 to 7 the RAD and the model parameters are shown one by one. What’s more, the measured and calculated data are illustrated in Figures 4−10 for comparison. We can see that all RAD values are less than 2.5%, which shows the correlated results are in excellent agreement with experimental values, and the modified Apelblat equation could be applied to correlate the solubilities of 3-M-4-NBA, 3-M-2-NBA, and 5-M-2-NBA in these above pure solvents. NRTL Correlation. For the studied binary systems, the solid−solid phase transition does not apply here. Thus, the

Figure 3. Comparison between experimental solubility of 3-M-4-NBA in n-propanol with the literature data: □, the measured solubility; Δ, literature data from Wu; S is defined as the mass of solute (g) in 100 g solvent.

Table 3. Solubility Values of 3-M-2-NBA in Different Pure Solvents at Different Temperatures and Pressure p = 101.3 kPaa,b T/K 300.55 308.95 317.15 321.85 324.35

S/(g/100g) 0.0357 0.0530 0.0739 0.0882 0.0961

Sc1/(g/100g) 0.0357 0.0530 0.0738 0.0897 0.0996

RD1/% −0.08 0.00 −0.10 1.67 3.61

Sc2/(g/100g) 0.0359 0.0518 0.0734 0.0892 0.0989

301.15 307.25 309.75 312.45 315.35 317.35

15.63 18.78 20.16 21.89 23.62 25.11

15.66 18.74 20.16 21.79 23.69 25.08

0.19 −0.19 −0.02 −0.42 0.29 −0.09

15.63 18.75 20.14 21.91 23.62 25.10

302.35 306.65 310.95 313.45 317.75 323.15

10.98 12.34 13.99 15.52 17.82 20.64

10.84 12.44 14.27 15.44 17.67 20.90

−1.29 0.83 2.02 −0.53 −0.86 1.23

11.04 12.33 13.97 15.45 17.75 20.74

302.25 310.15 315.05 318.05 320.95 324.25

6.135 7.975 9.199 10.43 11.67 13.01

6.097 7.986 9.443 10.47 11.56 12.95

−0.61 0.14 2.66 0.33 −0.98 −0.50

6.151 7.919 9.226 10.38 11.61 12.98

306.35 312.05 316.05 318.65

0.7763 0.9146 1.056 1.196

0.7554 0.9336 1.084 1.196

−2.69 2.08 2.73 −0.04

0.7492 0.9468 1.065 1.184

RD2/%

T/K

Water 0.64 327.65 −2.29 332.95 −0.72 337.85 1.17 341.95 2.88 347.15 Methanol −0.02 319.35 −0.14 322.45 −0.09 325.35 0.09 327.95 0.00 330.55 −0.04 Ethanol 0.54 326.25 −0.10 329.75 −0.14 333.45 −0.50 337.05 −0.39 340.15 0.46 343.35 n-Propanol 0.27 328.25 −0.70 332.45 0.30 335.15 −0.45 337.55 −0.51 341.65 −0.21 344.35 Formic Acid −3.50 329.95 3.52 334.05 0.93 337.65 −1.00 341.55 3363

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

RD2/%

0.1180 0.1458 0.1771 0.2138 0.2631

0.1145 0.1436 0.1775 0.2124 0.2673

−3.00 −1.53 0.23 −0.66 1.58

0.1148 0.1436 0.1767 0.2118 0.2655

−2.69 −1.48 −0.25 −0.93 0.92

26.58 28.90 31.27 33.99 36.42

26.55 28.99 31.45 33.83 36.37

−0.10 0.32 0.58 −0.46 −0.13

26.58 28.94 31.26 33.98 36.34

0.01 0.17 −0.02 0.00 −0.20

23.16 25.71 29.10 31.75 34.95 38.60

22.99 25.60 28.66 31.98 35.13 38.70

−0.71 −0.45 −1.50 0.72 0.50 0.24

23.19 25.81 29.05 31.93 34.98 38.32

0.15 0.38 −0.15 0.57 0.09 −0.74

14.97 16.95 18.89 20.84 23.39 25.85

14.86 17.18 18.86 20.50 23.65 26.00

−0.76 1.33 −0.18 −1.65 1.11 0.59

15.00 17.14 19.00 20.78 23.46 25.64

0.18 1.11 0.56 −0.30 0.26 −0.81

1.864 2.184 2.503 2.842

1.834 2.145 2.462 2.860

−1.6 −1.78 −1.62 0.62

1.819 2.137 2.455 2.854

−2.45 −2.16 −1.89 0.43



Article

Table 3. continued T/K

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

322.95 327.35

1.419 1.646

1.406 1.662

−0.90 0.97

1.422 1.660

302.65 308.85 314.45 319.15 322.65 327.25

2.268 2.702 3.147 3.602 4.090 4.695

2.256 2.703 3.185 3.656 4.052 4.641

−0.56 0.01 1.18 1.50 −0.92 −1.15

2.249 2.709 3.170 3.633 4.035 4.625

314.15 317.95 321.95 326.95 331.65 335.95

2.378 2.700 3.024 3.537 4.060 4.560

2.398 2.689 3.035 3.531 4.072 4.640

0.86 −0.40 0.36 −0.18 0.28 1.74

2.395 2.695 3.020 3.522 4.052 4.609

RD2/%

T/K

Formic Acid 0.20 344.85 0.86 Acetic Acid −0.86 332.05 0.24 335.15 0.73 339.95 0.87 343.75 −1.34 347.15 −1.49 Propanoic Acid 0.74 339.35 −0.20 342.35 −0.13 345.65 −0.42 348.55 −0.20 351.75 1.08

S/(g/100g)

Sc1/(g/100g)

3.195

3.247

1.61

3.254

1.83

5.313 5.940 6.743 7.511 8.366

5.348 5.862 6.759 7.567 8.372

0.66 −1.30 0.24 0.74 0.07

5.342 5.874 6.754 7.576 8.371

0.54 −1.10 0.17 0.87 0.06

5.110 5.669 6.242 6.807 7.448

5.145 5.637 6.233 6.809 7.508

0.69 −0.57 −0.14 0.03 0.82

5.118 5.629 6.219 6.786 7.485

0.16 −0.71 −0.37 −0.32 0.50

RD1/%

Sc2/(g/100g)

RD2/%


Table 4. Solubility Values of 5-M-2-NBA in Different Pure Solvents at Different Temperatures and Pressure p = 101.3 kPaa,b T/K

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

RD2/%

T/K

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

RD2/%

Water 315.55 319.95 322.95 326.15 327.95 331.15

0.9005 1.083 1.258 1.435 1.608 1.852

0.9059 1.092 1.248 1.447 1.576 1.843

−0.59 −0.75 0.85 −0.81 2.00 0.45

0.9041 1.105 1.206 1.407 1.608 1.810

304.35 307.75 311.25 314.65

219.4 231.3 243.3 255.6

219.9 230.9 243.1 255.8

0.22 −0.16 −0.08 0.07

219.9 230.6 242.9 255.8

301.95 304.75 307.45 310.25 313.45

149.4 156.5 163.2 169.4 178.4

149.5 156.2 162.8 170.0 178.6

0.12 −0.19 −0.19 0.36 0.12

149.67 156.04 162.72 170.29 178.65

305.15 309.45 312.75 315.65 319.35 322.65

111.0 119.3 126.0 132.8 142.1 151.5

110.7 119.4 126.5 133.1 142.0 150.5

−0.23 0.05 0.36 0.18 −0.06 −0.68

110.7 119.4 126.6 133.2 142.0 150.0

308.55 311.15 314.75 317.25 319.65 321.65

17.26 19.41 22.21 25.05 27.89 30.68

17.17 19.21 22.46 25.06 27.87 30.47

−0.49 −1.01 1.10 0.04 −0.06 −0.69

17.34 19.37 22.29 25.03 27.85 30.58

307.15 309.95 313.65 317.15 320.75

39.88 43.68 48.75 54.19 59.65

40.12 43.49 48.43 53.69 59.78

0.61 −0.44 −0.66 −0.93 0.20

39.89 43.69 48.70 54.11 59.61

0.39 334.55 2.02 336.85 −4.17 339.35 −1.96 341.35 0.00 343.55 −2.26 Methanol 0.22 317.75 −0.29 320.35 −0.16 322.95 0.06 325.45 Ethanol 0.21 316.75 −0.27 320.15 −0.26 323.95 0.52 326.95 0.14 329.75 n-Propanol −0.23 326.45 0.07 330.35 0.48 333.95 0.25 337.35 −0.07 340.45 −1.00 Formic Acid 0.47 323.45 −0.20 326.15 0.34 329.45 −0.08 331.65 −0.11 334.45 −0.32 Acetic Acid 0.05 324.05 0.02 326.35 −0.10 329.35 −0.14 332.35 −0.07 334.65 3364

2.142 2.437 2.795 3.151 3.572

2.189 2.467 2.817 3.139 3.543

−2.19 −1.24 −0.79 0.37 0.81

2.112 2.414 2.818 3.121 3.525

−1.41 −0.92 0.81 −0.95 −1.33

267.4 279.2 291.3 303.3

268.3 279.5 291.3 303.3

0.34 0.07 −0.03 0.01

268.5 279.4 291.0 303

0.42 0.04 −0.11 −0.10

188.2 198.4 209.7 219.2 229.7

187.9 198.0 209.9 219.8 229.4

−0.14 −0.22 0.06 0.25 −0.14

187.7 197.6 209.9 220.0 229.4

−0.25 −0.39 0.06 0.38 −0.12

160.8 172.3 184.1 195.6 207.2

161.0 172.5 184.0 195.7 207.1

0.10 0.12 −0.03 0.05 −0.04

161.1 172.7 184.1 195.8 207.1

0.18 0.19 0.01 0.10 −0.02

33.57 37.61 43.08 48.46 55.03

33.03 37.33 43.43 48.11 54.9

−1.61 −0.77 0.81 −0.71 −0.22

33.34 37.55 43.34 48.49 55.20

−0.68 −0.17 0.60 0.07 0.31

65.42 70.83 78.05 85.40 92.76

66.06 70.89 77.82 85.57 92.14

0.98 0.08 −0.29 0.20 −0.67

65.50 70.90 78.07 85.53 92.57

0.13 0.09 0.03 0.15 −0.21



Article

Table 4. continued T/K 302.95 305.35 308.65 311.75 315.15 318.15

S/(g/100g) 24.22 25.99 28.70 32.13 35.68 39.56

Sc1/(g/100g) 24.07 26.01 28.95 32.03 35.82 39.55

RD1/% −0.61 0.07 0.88 −0.30 0.40 −0.01

Sc2/(g/100g) 24.21 26.00 28.69 32.09 35.70 39.58

RD2/%

T/K

Propanoic Acid −0.01 321.75 0.02 324.95 −0.03 327.85 −0.12 330.65 0.07 333.75 0.05

S/(g/100g)

Sc1/(g/100g)

RD1/%

Sc2/(g/100g)

RD2/%

44.83 49.86 55.11 60.40 67.19

44.61 49.70 54.88 60.47 67.44

−0.50 −0.31 −0.41 0.13 0.38

44.82 49.91 55.10 60.45 67.13

−0.02 0.10 −0.01 0.08 −0.08


Figure 4. Solubility values of different solutes in water at different temperatures and under atmospheric pressure: □, 3-M-4-NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

Figure 7. Solubility values of different solutes in n-propanol at different temperatures and under atmospheric pressure: □, 3-M-4NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

Figure 5. Solubility values of different solutes in methanol at different temperatures and under atmospheric pressure: □, 3-M-4-NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

Figure 8. Solubility values of different solutes in formic acid at different temperatures and under atmospheric pressure: □, 3-M-4NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

Figure 6. Solubility values of different solutes in ethanol at different temperatures and under atmospheric pressure: □, 3-M-4-NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

Figure 9. Solubility values of different solutes in acetic acid at different temperatures and under atmospheric pressure: □, 3-M-4-NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

solid−liquid equilibrium can be described by following equation25,26

where γ1 and x1 are the activity coefficient and molar fraction of solute, ΔfusH and Tfus are the fusion enthalpy and fusion point of solute, the molar gas constant R is equal to 8.314 J·mol−1·K−1, and T is the Kelvin temperature of the solution. In this work, the fusion enthalpy and fusion point of 5-M-2-NBA are

ln(γ1x1) = −

ΔfusH ⎛ 1 1 ⎞ ⎜ − ⎟ R ⎝T Tfus ⎠

(3) 3365



Article

22590 J·mol−1 and 408.50 K, and those for 3-M-2-NBA are 37770 J·mol−1 and 494.93K. As for 3-M-4-NBA, ΔfusH = 33770 J·mol−1 and Tfus = 489.11 K. All these values can be obtained

from the literature reported by Monte.27 In this work, the NRTL model equation28−30 is adopted to calculate the activity coefficient γ1. The equation is shown below 2

ln(γi) =

∑ j = 1 τjiGjixj 2

∑k = 1 Gkixk

2

+

∑ j=1

2 ⎛ ∑ τ G x⎞ ⎜τ − k = 1 kj ki j ⎟ ij 2 2 ∑k = 1 Gkjxk ⎜⎝ ∑k = 1 Gkjxk ⎟⎠

Gijxj

(4)

τij = aij +

bij (5)

T

Gij = exp( −αijτij)

αij = αji , Figure 10. Solubility values of different solutes in propanoic acid at different temperatures and under atmospheric pressure: □, 3-M-4NBA; ●, 3-M-2-NBA; ▲, 5-M-2-NBA; black solid line, Apelblat equation correlated; red dotted line, NRTL model correlated.

solvents

A

B

C

RAD/%

−63.532 −34.812 −214.17 5.3143 −1.1910 −14.918 −18.745

−983.28 −1349.3 7134.6 −3524.4 −3761.0 −2106.5 −1934.9

9.7478 6.0799 32.603 0.32013 1.2373 2.9973 3.5805

1.13 0.49 0.37 0.70 0.89 0.95 0.71

A

B

C

RAD/%

water methanol ethanol n-propanol formic acid acetic acid propanoic acid

−183.77 −49.398 −54.117 −118.51 −183.52 −123.89 −124.88

4506.8 −172.67 −174.97 2559.6 5125.1 3113.6 3086.2

27.787 8.1221 8.9427 18.581 28.042 19.028 19.204

1.54 0.24 0.94 0.86 1.51 0.75 0.54


A −584.48 −55.301 −4.9436 −9.7903 −186.93 −90.124 −80.522

B 23501 1640.2 −709.54 −631.12 5090.8 1983.8 1228.8

C

solvents

a12

a21

b12/K

b21/K

RAD/%


−1.4716 1.2468 0.6359 0.6143 1.0402 0.8254 0.1998

5.4189 −4.9404 0.0001 −1.2726 −3.3461 −0.6229 1.4842

−596.9 −1315.3 −1131.1 −1115.8 −1128.1 −979.3 −771.8542

2615.8 4015.7 2092.7 2426.2 3036.5 1426 746.749

1.37 0.08 0.32 0.42 1.34 0.69 0.47

Table 10. Parameters of the NRTL Models for 5-M-2-NBA in Different Solvents

Table 7. Parameters of the Modified Apelblat Equation for 5-M-2-NBA in Different Solvents solvents

(7)

Table 9. Parameters of the NRTL Models for 3-M-2-NBA in Different Solvents

Table 6. Parameters of the Modified Apelblat Equation for 3-M-2-NBA in Different Solvents solvents

τii = 0

where γi and xi are the activity coefficient and molar fraction of the component i, and T is the Kelvin temperature. According to the recommendation of Prausnitz, αij in eq 7 is constant value 0.3.30 aij and bij are the NRTL model parameters and are listed in Tables 8 to 10, which are also optimized by function fminsearch in Matlab, and the function is the same with eq 2. The corresponding RD and the relative average deviation RAD can be found in Tables 2 to 4 and Tables 8 to 10, respectively. The solubility data calculated by the NRTL model are shown in Tables 2 to 4 and Figures 4 to 10. By comparison, we can find all RAD values are less than 2%, which indicates the correlated solubilities are in excellent agreement with the measured solubility values.

Table 5. Parameters of the Modified Apelblat Equation for 3-M-4-NBA in Different Solvents water methanol ethanol n-propanol formic acid acetic acid propanoic acid

τij ≠ τji ,

(6)

RAD/%

solvents

a12

a21

b12/K

b21/K

RAD/%

0.98 0.09 0.12 0.12 0.63 0.42 0.31


1.4662 6.8683 4.7439 10.5669 4.5770 −0.0641 3.0245

−5.1315 0.4979 1.5971 −0.0431 −11.5015 −22.5841 −4.9745

−1151.7 −1833.6 −511.7 −2493.8 −1889.7 −360.1 −1470.9

4630 −771.5 −1298.5 −737.0 4852.5 9504.5 3026.5

0.44 0.12 0.18 0.16 0.29 0.08 0.05

87.411 8.5060 1.0515 1.8431 29.180 14.234 12.961

Table 8. Parameters of the NRTL Models for 3-M-4-NBA in Different Solvents solvents

a12

a21

b12/K

b21/K

RAD/%


59.5448 −0.2655 1.5006 −1.0344 −0.6950 45.893 47.6022

11.2504 1.3190 −6.4511 2.1088 2.4124 6.7097 6.7917

−17301 −510.8841 −1283.3 −250.0238 −73.8569 −12530 −13241

−2019.0 493.1053 3747.8 158.6924 81.5521 −2495 −2567

0.81 0.48 0.27 0.69 0.81 0.81 0.55

3366



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(12) Wepster, B. M. Steric effects on mesomerism. XVI. Comparative investigations involving ultraviolet absorption spectra, molecular refractions, rates of reactions, and basic strengths of aromatic amines. Recl. Trav. Chim. Pays-Bas 1957, 76, 357−389. (13) Muller, E. Zur kenntnis der m-toluylsaure. Ber. Dtsch. Chem. Ges. 1909, 42, 423−434. (14) Heravi, M. M.; Farhangi, N.; Bakhtiari, K.; et al. Oxidation of primary alcohols to carboxylic acids using silica supported CrO3/ H5IO6 under microwave irradiation in a solvent-free system. J. Chin. Chem. Soc. 2006, 53, 643−645. (15) Wu, Y.; Qin, Y.; Bai, L.; Kang, Y.; Zhang, Y. Solubility of 3methyl-4-nitrobenzoic acid in binary solvent mixtures of {(1,4-dioxane, N-methyl-2-pyrrolidone, N,N-dimethylformamide) + methanol} from T = (283.15 to 318.15) K: Experimental determination and thermodynamic modelling. J. Chem. Thermodyn. 2017, 105, 165−172. (16) Wu, Y.; Di, Y.; Zhang, X.; Zhang, Y. Solubility determination and thermodynamic modeling of 3-methyl-4-nitrobenzoic acid in twelve organic solvents from T = (283.15−318.15) K and mixing properties of solutions. J. Chem. Thermodyn. 2016, 102, 257−269. (17) Acree, W. E., Jr.; Bowen, K. R.; Horton, M. Y.; Abraham, M. H. Computation of Abraham model solute descriptors for 3-methyl-4nitrobenzoic acid from measured solubility data. Phys. Chem. Liq. 2017, 55 (4), 482−491. (18) Li, X.; Wang, M.; Du, C.; Cong, Y.; Zhao, H. Thermodynamic functions for solubility of 3-nitro-o-toluic acid in nine organic solvents from T = (283.15 to 318.15) K and apparent thermodynamic properties of solutions. J. Chem. Thermodyn. 2017, 110, 87−98. (19) Hart, E.; Ramirez, A. M.; Cheeran, S.; Barrera, M.; Horton, M. Y.; Wadawadigi, A.; Acree, W. E., Jr.; Abraham, M. H. Determination of abraham model solute descriptors for 2-methyl-3-nitrobenzoic acid from measured solubility data in alcohol, alkyl ether, alkyl acetate and 2-alkoxyalcohol mono-solvents. Phys. Chem. Liq. 2017, 55, 1−9. (20) Jiang, Q.; Gao, G. H.; Yu, Y. X.; Qin, Y. Solubility of sodium dimethyl isophthalate-5-sulfonate in water and in water plus methanol containing sodium sulfate. J. Chem. Eng. Data 2000, 45, 292−294. (21) Chen, M. M.; Ma, P. S. Solid-liquid equilibria of several systems containing acetic acid. J. Chem. Eng. Data 2004, 49, 756−759. (22) Apelblat, A.; Manzurola, E. Solubilities of o-acetylsalicylic, 4aminosalicylic, 3,5-dinitrosalicylic, and p-toluic acid, and magnesiumDL-aspartate in water from T = (278 to 348) K. J. Chem. Thermodyn. 1999, 31, 85−91. (23) Manzurola, E.; Apelblat, A. Solubilities of L-glutamic acid, 3nitrobenzoic acid, p-toluic acid, calcium-L-lactate, calcium gluconate, magnesium-DL-aspartate, and magnesium-L-lactate in water. J. Chem. Thermodyn. 2002, 34, 1127−1136. (24) Nelder, J. A.; Mead, R. A. Simplex method for function minimization. Comput. J. 1965, 7, 308−313. (25) Shen, Z. P.; Wang, Q. B.; Chen, L. H.; Sheng, X. X.; Pei, Y. C. Solubilities of phthalic acid and o-toluic acid in binary acetic acid + water and acetic acid + o-xylene solvent mixtures. J. Chem. Eng. Data 2016, 61, 3233−3240. (26) Luo, W. P.; Ruan, D.; Liu, D. W.; Xie, K. L.; Li, X. Q.; Deng, W.; Guo, C. C. Measurement and correlation for solubilities of adipic acid in acetic acid + ε-caprolactone mixtures and cyclohexanone + εcaprolactone mixtures. J. Chem. Eng. Data 2016, 61, 2474−2480. (27) Monte, M. J. S.; Hillesheim, D. M. Thermodynamic study on the sublimation of six methylnitrobenzoic acids. J. Chem. Thermodyn. 2001, 33, 103−112. (28) Wang, H.; Wang, Q. B.; Xiong, Z. H.; Chen, C. X.; Shen, B. W. Solubilities of benzoic acid in binary (benzyl alcohol + benzaldehyde) solvent mixtures. J. Chem. Thermodyn. 2015, 83, 61−66. (29) Wang, H.; Wang, Q. B.; Xiong, Z. H.; Chen, C. X.; Shen, B. W. Solubilities of benzoic acid in binary methylbenzene + benzyl alcohol and methylbenzene + benzaldehyde solvent mixtures. J. Chem. Eng. Data 2015, 60, 643−652. (30) Prausnitz, J. M.; Lichtenthaler, R. N.; Azevedo, E. G. D. Molecular Thermodynamics of Fluid-Phase Equilibria, 3rd ed.; Prentice Hall: Beijing, 1999.

4. CONCLUSIONS The solubilities of 3-M-4-NBA, 3-M-2-NBA, and 5-M-2-NBA in water, methanol, ethanol, n-propanol, formic acid, acetic acid, and propanoic acid were measured at various temperatures and under atmospheric pressure, respectively. Three solutes all have small solubilities in water although they are easy to dissolve in acids and alcohols. Because there is a big difference between the solubilities of 5-M-2-NBA and other two solutes in all three solvents, it is easy to separate 5-M-2-NBA from the crude product through crystallization. However, 3-M-4-NBA and 3-M-2NBA have a solubility difference in alcohols, although it is not large. If they need to be separated, more single or mixed solvents are needed to be tested.

■

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Ze Tan: 0000-0002-7156-5063 Funding

The project is supported by the National Nature Science Fund (21302049). The authors would like to thank NSFC for the financial support. Notes

The authors declare no competing financial interest.

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REFERENCES

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Study on the Solubilities of Mononitro-Substituted Products of Nitration

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