Solubility Behavior of 2-Chloro-3- (trifluoromethyl)pyridine in (Ethyl

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

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Solubility Behavior of 2‑Chloro-3- (trifluoromethyl)pyridine in (Ethyl Acetate + n‑Butanol, DMF + n‑Butanol, DMF + Ethanol) Solvent Mixtures Liqing Zhao, Bing Zhang, and Li Xu*

J. Chem. Eng. Data Downloaded from pubs.acs.org by TULANE UNIV on 02/16/19. For personal use only.

School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, People’s Republic of China ABSTRACT: The solubility of 2-chloro-3-(trifluoromethyl)pyridine in ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol solvent mixtures was determined via an isothermal static method within the temperature scope of 263.15−303.15 K under 101.3 KPa. The solubility of 2-chloro-3-(trifluoromethyl)pyridine increased with increasing temperature and mass fraction of ethyl acetate or DMF in the binary solvent systems. The modified Apelblat model, Jouyban−Acree model, and Sun model were used to correlate the solubility data of 2-chloro-3-(trifluoromethyl)pyridine in the binary mixtures. The values of RD and RMSD indicated that three models fit the solubility data quite well, and the Sun model gave the best correlation of the solubility data in the binary ethyl acetate + n-butanol and DMF + n-butanol solvents. The Apelblat model gave the best correlation of the solubility data in the binary DMF + ethanol solvent.

1. INTRODUCTION 2-Chloro-3-(trifluoromethyl)pyridine (C6H3ClF3N, white crystal, CAS registry no 65753-47-1, molar mass 181.54 g·mol−1) is a useful chemical for an intermediate, and it usually has been used in the synthesis of medicine and pesticide.1 2-Chloro-3(trifluoromethyl)pyridine is used to synthesize high-efficiency and low-residue pesticides, such as fluazifop-butyl, poppenatemethyl, and flazasulfuron. This kind of efficient and low-residue fluorine-containing pesticide is environmentally friendly. In our team, 2-chloro-3-(trifluoromethyl)pyridine was used to make ordered mesoporous carbon material; ordered mesoporous carbon material was made via the impregnation method.2,3 In our team, 2-chloro-3-(trifluoromethyl)pyridine was needed to dissolve in some pure or binary solvents.2,3 But the solubility behavior of 2-chloro-3-(trifluoromethyl)pyridine in our selected binary solvents (ethyl acetate + n-butanol, DMF + n-butanol, DMF + ethanol) was not found yet. In Wang et al.’s paper,4 they measured the solubility of 2-chloro-3-(trifluoromethyl)pyridine in methylbenzene, dichloromethane, ethanol, n-propanol, n-hexane, n-heptane, and ethanol + n-propanol mixtures. In order to further know the solubility behavior of 2-chloro-3-(trifluoromethyl)pyridine in mixed solvent, we measured the solubility of 2-chloro-3-(trifluoromethyl)pyridine in binary (ethyl acetate + n-butanol, DMF + n-butanol, DMF + ethanol) solvents. In addition, the solubility data are important for the process of crystallization. The mixed solvents may change the solubility of 2-chloro-3-(trifluoromethyl)pyridine. To select an appropriate solvent system, the objective of the present work was to measure and correlate the solubility data of 2-chloro-3-(trifluoromethyl)pyridine in the binary solvents mixtures of ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol. In this paper, because of the low melting point (melting point: 312.19 K; melting enthalpy = 19.23 kJ·mol−1; from Neway Chemicals Co., Ltd.) and high solubility in ethyl © XXXX American Chemical Society

acetate and n-butyl alcohol, the solubility of 2-chloro-3(trifluoromethyl)pyridine in binary (ethyl acetate + n-butanol, DMF + n-butanol, DMF + ethanol) solvent mixtures was measured experimentally at temperatures ranging from 263.15 to 303.15 K under atmospheric pressure. The solubility data were correlated via the Jouyban−Acree model,5 the modified Apelblat model,6 and the Sun model.6,7

2. EXPERIMENTAL SECTION 2.1. Chemicals and Equipment. The purity of 2-chloro-3(trifluoromethyl)pyridine (mass fraction ≥ 0.995) was determined by gas phase chromatography (GC type: Agilent GC7890B). Ethyl acetate, n-butyl alcohol, N,N-dimethylformamide (DMF), and analytical grade ethanol were used in the experiment without additional purification. The purity of solvents was measured by GC (GC type: Agilent GC7890B); the mass fraction purities of selected solvents were 0.9975 (ethyl acetate), 0.9980 (n-butyl alcohol), 0.9981 (DMF), and 0.9973 (ethanol), respectively. A detailed description of the solvents is shown in Table 1. The constant-temperature water bath (type, DC4006; precision, ±0.01 K), which was produced by Shanghai Bilon Precision Instrument Co., Ltd., was used to maintain the temperature. The analytical balance used in the experiment was provided by Shenzhen Shengmei Instrument Co., Ltd. and had an uncertainty of ±0.0001 g. The water was stirred using a magnetic stirring (Shanghai Mei Yingpu instrument and Meter Manufacturing Co., Ltd.); the rotational speed of magnetic stirring was 260 r/min. The concentration of the sample was analyzed by GC. GC conditions: The capillary column was an HP-5 column Received: October 29, 2018 Accepted: February 1, 2019

A

DOI: 10.1021/acs.jced.8b00989 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Purity and Sources of Solute and Solvents chemical name

ω1 =

mass fraction purity

source

≥0.995a ≥0.990a

Neway Chemicals Co., LTD Tianjin Jiangtian Chemical Co., LTD

≥0.995a ≥0.995a ≥0.995a

Tianjin Jiangtian Chemical Co., LTD Tianjin Jiangtian Chemical Co., LTD Tianjin Jiangtian Chemical Co., LTD

C6H3ClF3N N,Ndimethylformamide ethanol ethyl acetate (EAC) n-butanol

3. RESULTS AND DISCUSSION 3.1. The Comparison between the Experimental Data and Reference Data. The experimental solubility data and reference solubility data of 2-chloro-3-(trifluoromethyl)pyridine in ethyl acetate, n-butanol, and ethanol are listed in Table 2. The values of RD were less than 0.0498, which indicated that the experimental equipment and method were reliable. The literature data4,24 and experimental mole fraction solubility data are plotted in Figure 1.

Determined by GC (gas chromatography).

(30 m × 0.32 mm). Temperatures: injector, 473 K; FID, 423 K. Carrier gas: N2; flow rate, 25 mL·min−1. Temperature program: from 323.15 K (0 min) to 493.15 K (20 min) at 8.5 K × min−1. Injection mode, split; split ratio, 10:1; injection volume, 1 μL. 2.2. Preparation of Solvent Mixtures. The binary (ethyl acetate + n-butanol, DMF + n-butanol, DMF + ethanol) solvent mixtures were prepared by means of an analytical balance. The amount of mixed solvent was about 50 g, and the precision was estimated to ±0.0001 g. The mass fractions of ethyl acetate in the binary mixtures prepared varied from 0 to 1.0. The Erlenmeyer flask was covered with a stopper to prevent the solvent from escaping during the preparation of solvent mixtures. During the experiment, the atmospheric pressure was 101.3 kPa. 2.3. Solubility Measurement. In the present work, the solubility of 2-chloro-3-(trifluoromethyl)pyridine in binary solvent mixtures of ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol were determined via an isothermal static equilibrium method, which was previously described in many works.8−10 First, an excessive amount of 2-chloro-3(trifluoromethyl)pyridine and about 5 mL of solvent (prepared binary solvent mixtures) were added into a doubled jacketed glass container. The double jacketed glass vessel was kept at the desired temperature, which was controlled with a thermostatic water bath. The actual temperature was shown using a mercury thermometer (precision, 0.01 K) in the jacketed glass vessel. The mixture was stirred via magnetic stirring for over 24 h. Then, after that, the mixture was kept static for 12 h. At last, the concentration of the upper portion clear solution was analyzed using GC. Every analysis was carried out three times, and the average values were considered as the final values. The mole fraction solubility of 2-chloro-3-(trifluoromethyl)pyridine in the binary solvent mixtures are based on eq 1, and the composition of binary mixtures (ω) was defined using eq 2: m3 /M3 m1/M1 + m2 /M 2 + m3 /M3

(2)

in which m1 and m2 represent the masses of solvents and m3 represents the masses of 2-chloro-3-(trifluoromethyl)pyridine, respectively. Furthermore, M1, M2, and M3 are the corresponding molar masses.

a

x=

m1 m2 + m1

Figure 1. Comparison between the experimental data and reference data (“exp” and “ref” represent experimental data and reference data, respectively).

3.2. Solubility Data. The mole fraction solubilities of 2-chloro-3-(trifluoromethyl)pyridine in binary solvent mixtures of ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol at different temperature (263.15 to 303.15 K) are summarized in Tables 3, 4, and 5. The graphs of corresponding mole fraction solubility against temperature and solvent composition are shown in Figures 2, 3, and 4. The figures and tables show that

(1)

Table 2. Comparison between the Experimental Data and Reference Data n-butanol

ethyl acetate T/K 263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

xa

xexp

0.3951 0.4516 0.5104 0.5836 0.6567 0.7378 0.8227

0.3063 0.3499 0.3991 0.4546 0.5084 0.5826 0.6517 0.7388 0.8237

RD/%

−1.01 −0.66 0.39 0.17 0.76 −0.14 −0.12

xa

xexp

0.1449 0.1875 0.2308 0.2858 0.3480 0.4235 0.5002

0.0947 0.1184 0.1401 0.1835 0.2285 0.2838 0.3453 0.4215 0.5102

ethanol RD/%

3.31 2.13 1.00 0.70 0.78 0.47 −2.00

xb

xexp

RD/%

0.1366 0.1818 0.2530 0.3553 0.4753 0.6350 0.8747

0.0807 0.1115 0.1406 0.1858 0.2623 0.3633 0.4763 0.6205 0.8311

−2.93 −2.20 −3.68 −2.25 −0.21 2.28 4.98

a

The values from ref 24. bThe values from ref 4. B



Article

Table 3. Mole Fraction Solubility Data (xcal) of 2-Chloro-3-(trifluoromethyl)pyridine in Binary Ethyl Acetate(ω1) + n-butanol(1 − ω1) Mixtures (P = 0.1 MPa)a modified Apelblat T/K

x

xcal

RD/%

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.0947 0.1184 0.1401 0.1835 0.2285 0.2838 0.3453 0.4215 0.5102

0.0912 0.1161 0.1466 0.1836 0.2283 0.2819 0.3457 0.4213 0.5103

3.65 1.91 −4.64 −0.07 0.08 0.68 −0.11 0.06 −0.01

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1391 0.1716 0.2076 0.2505 0.3075 0.3692 0.4413 0.5189 0.5979

0.1392 0.1716 0.2099 0.2546 0.3066 0.3667 0.4356 0.5142 0.6034

−0.09 −0.04 −1.08 −1.65 0.30 0.68 1.30 0.90 −0.92

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1817 0.2148 0.2457 0.3023 0.3482 0.4123 0.4829 0.5598 0.6446

0.1773 0.2123 0.2527 0.2992 0.3523 0.4127 0.4811 0.5583 0.6451

2.40 1.16 −2.87 1.04 −1.17 −0.08 0.37 0.28 −0.07

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.2123 0.2517 0.2909 0.3442 0.4075 0.4762 0.5467 0.6284 0.7092

0.2115 0.2512 0.2965 0.3479 0.4059 0.4711 0.5439 0.6250 0.7148

0.36 0.19 −1.95 −1.08 0.39 1.07 0.51 0.54 −0.80

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.2574 0.3004 0.3432 0.4036 0.4592 0.5336 0.6091 0.6878 0.7663

0.2568 0.3000 0.3486 0.4028 0.4631 0.5298 0.6034 0.6842 0.7726

0.24 0.12 −1.57 0.21 −0.84 0.72 0.94 0.53 −0.82

263.15 268.15 273.15 278.15 283.15 288.15 293.15

0.3063 0.3499 0.3991 0.4546 0.5084 0.5826 0.6517

0.3035 0.3485 0.3985 0.4538 0.5147 0.5817 0.6551

0.91 0.40 0.16 0.19 −1.24 0.16 −0.52

Jouyban−Acree model xcal

RD/%

Sun model xcal

RD/%

ω1 = 0 0.0947 0.1184 0.1401 0.1835 0.2285 0.2838 0.3453 0.4215 0.5102

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0954 0.1202 0.1501 0.1859 0.2286 0.2791 0.3383 0.4076 0.4880

−0.74 −1.52 −7.14 −1.31 −0.04 1.66 2.03 3.30 4.35

0.1365 0.1676 0.1964 0.2504 0.3052 0.3728 0.4459 0.5361 0.6382

1.85 2.31 5.40 0.03 0.76 −0.98 −1.04 −3.32 −6.75

0.1378 0.1701 0.2084 0.2534 0.3061 0.3672 0.4379 0.5190 0.6118

0.92 0.85 −0.38 −1.17 0.47 0.54 0.77 −0.03 −2.33

0.1689 0.2038 0.2373 0.2948 0.3523 0.424 0.4993 0.5921 0.6942

7.02 5.13 3.42 2.49 −1.18 −2.83 −3.40 −5.76 −7.69

0.1707 0.2070 0.2492 0.2980 0.3541 0.4183 0.4914 0.5741 0.6672

6.03 3.64 −1.42 1.43 −1.70 −1.45 −1.77 −2.55 −3.50

0.2073 0.2459 0.2845 0.3440 0.4026 0.4772 0.5530 0.6466 0.7463

2.34 2.30 2.19 0.05 1.21 −0.22 −1.15 −2.90 −5.23

0.2099 0.2498 0.2954 0.3473 0.4058 0.4717 0.5455 0.6278 0.7192

1.11 0.75 −1.56 −0.90 0.42 0.94 0.22 0.09 −1.41

0.2506 0.2930 0.3369 0.3984 0.4584 0.5364 0.6133 0.7087 0.8073

2.64 2.46 1.83 1.30 0.17 −0.52 −0.69 −3.03 −5.35

0.2541 0.2977 0.3468 0.4017 0.4630 0.5310 0.6062 0.6889 0.7797

1.28 0.90 −1.05 0.48 −0.83 0.49 0.48 −0.15 −1.74

0.3063 0.3499 0.3991 0.4546 0.5084 0.5826 0.6517

0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.3113 0.3557 0.4043 0.4575 0.5155 0.5784 0.6464

−1.63 −1.66 −1.30 −0.64 −1.40 0.72 0.81

ω1 = 0.2857

ω1 = 0.4445

ω1 = 0.6406

ω1 = 0.8261

ω1 = 1.0000

C



Article

Table 3. continued modified Apelblat T/K

x

cal

x

Jouyban−Acree model cal

x

RD/%

RD/%

Sun model cal

x

RD/%

ω1 = 1.0000 298.15 303.15

0.7388 0.8237

0.7353 0.8227

0.48 0.12

0.7388 0.8237

0.00 0.00

0.7198 0.7986

2.57 3.05

The standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur(x) = 0.06, and ur(ω) = 0.05. ω is the mass-fraction composition of the mixed solvent. a

Table 4. Mole Fraction Solubility Data (xcal) of 2-Chloro-3-(trifluoromethyl)pyridine in Binary DMF(ω1) + n-Butanol(1 − ω1) Mixtures (P = 0.1 MPa)a modified Apelblat T/K

x

xcal

RD/%

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.0895 0.1144 0.1401 0.1835 0.2285 0.2838 0.3453 0.4215 0.5102

0.0912 0.1161 0.1466 0.1836 0.2283 0.2819 0.3457 0.4213 0.5103

−1.96 −1.50 −4.64 −0.07 0.08 0.68 −0.11 0.06 −0.01

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1566 0.1913 0.2290 0.2805 0.3355 0.3968 0.4653 0.5455 0.6403

0.1571 0.1916 0.2319 0.2788 0.3330 0.3953 0.4665 0.5475 0.6393

−0.31 −0.16 −1.28 0.62 0.76 0.39 −0.26 −0.37 0.17

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1970 0.2362 0.2783 0.3345 0.3940 0.4599 0.5330 0.6178 0.7126

0.1970 0.2362 0.2814 0.3331 0.3920 0.4587 0.5339 0.6183 0.7125

−0.01 0.00 −1.11 0.40 0.52 0.27 −0.16 −0.08 0.01

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.2351 0.2798 0.3243 0.3891 0.4574 0.5319 0.6137 0.7072 0.8020

0.2364 0.2813 0.3328 0.3912 0.4573 0.5317 0.6150 0.7080 0.8112

−0.55 −0.54 −2.59 −0.53 0.02 0.05 −0.22 −0.12 −1.15

263.15 268.15 273.15 278.15 283.15 288.15 293.15

0.2946 0.3445 0.3970 0.4642 0.5348 0.6117 0.6958

0.2952 0.3450 0.4009 0.4634 0.5329 0.6100 0.6950

−0.21 −0.13 −0.98 0.17 0.35 0.29 0.13

Jouyban−Acree model

Sun model

xcal

RD/%

xcal

RD/%

0.0947 0.1184 0.1401 0.1835 0.2285 0.2838 0.3453 0.4215 0.5102

−5.83 −3.48 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0950 0.1194 0.1489 0.1841 0.2260 0.2755 0.3335 0.4012 0.4796

−6.16 −4.36 −6.28 −0.33 1.09 2.92 3.42 4.82 6.00

0.1428 0.1788 0.2161 0.2752 0.3367 0.4115 0.4918 0.5906 0.7039

8.84 6.52 5.62 1.89 −0.36 −3.70 −5.70 −8.27 −9.93

0.1511 0.1863 0.2279 0.2768 0.3338 0.4000 0.4764 0.5641 0.6641

3.54 2.60 0.46 1.32 0.51 −0.81 −2.39 −3.41 −3.71

0.1787 0.2201 0.2637 0.3274 0.3949 0.4766 0.5613 0.6650 0.7826

9.29 6.83 5.25 2.11 −0.22 −3.63 −5.31 −7.64 −9.82

0.1886 0.2288 0.2757 0.3300 0.3924 0.4638 0.5452 0.6373 0.7412

4.26 3.15 0.94 1.33 0.42 −0.84 −2.29 −3.16 −4.01

0.2213 0.2680 0.3182 0.3847 0.4572 0.5446 0.6317 0.7382 0.8575

5.86 4.22 1.89 1.14 0.04 −2.38 −2.93 −4.39 −6.92

0.2327 0.2778 0.3295 0.3885 0.4553 0.5307 0.6154 0.7100 0.8153

1.01 0.72 −1.59 0.16 0.46 0.23 −0.28 −0.40 −1.66

0.2740 0.3269 0.3850 0.4553 0.5344 0.6295 0.7207

6.98 5.12 3.03 1.92 0.08 −2.91 −3.57

0.2873 0.3382 0.3958 0.4606 0.5332 0.6141 0.7038

2.47 1.84 0.31 0.77 0.30 −0.39 −1.14

ω1 = 0

ω1 = 0.2857

ω1 = 0.4445

ω1 = 0.6406

ω1 = 0.8261

D



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x

cal

x

Jouyban−Acree model cal

x

RD/%

RD/%

Sun model cal

x

RD/%

ω1 = 0.8261 298.15 303.15

0.7917 0.8865

0.7884 0.8906

0.42 −0.47

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.3245 0.3786 0.4412 0.5034 0.5796 0.6715 0.7536 0.8548 0.9657

0.3244 0.3786 0.4392 0.5069 0.5819 0.6648 0.7560 0.8560 0.9651

0.02 0.00 0.44 −0.69 −0.40 1.00 −0.32 −0.14 0.06

0.8323 0.9563

−5.13 −7.87

0.8030 0.9121

−1.43 −2.89

0.3063 0.3499 0.3991 0.4546 0.5084 0.5826 0.6517 0.7388 0.8237

5.61 7.58 9.54 9.69 12.28 13.24 13.52 13.57 14.70

0.3386 0.3557 0.4043 0.4575 0.5155 0.5784 0.6464 0.7198 0.7986

−4.35 −1.66 −1.30 −0.64 −1.40 0.72 0.81 2.57 3.05

ω1 = 1.0000

a The standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur(x) = 0.06, and ur(ω) = 0.05. ω is the mass-fraction composition of the mixed solvent.

Table 5. Mole Fraction Solubility Data (xcal) of 2-Chloro-3-(trifluoromethyl)pyridine in Binary DMF(ω1) + Ethanol(1 − ω1) Mixtures (P = 0.1 MPa)a modified Apelblat T/K

x

cal

x

Jouyban−Acree model x

RD/%

cal

RD/%

Sun model x

cal

RD/%

ω1 = 0 263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.0807 0.1115 0.1406 0.1858 0.2623 0.3633 0.4763 0.6205 0.8311

0.0774 0.1061 0.1446 0.1959 0.2640 0.3541 0.4724 0.6274 0.8294

4.03 4.83 −2.82 −5.43 −0.66 2.55 0.81 −1.11 0.21

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1390 0.1797 0.2328 0.2906 0.3656 0.4578 0.5724 0.7053 0.8553

0.1386 0.1794 0.2301 0.2923 0.3681 0.4599 0.5701 0.7016 0.8574

0.24 0.13 1.17 −0.59 −0.70 −0.46 0.39 0.52 −0.25

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.1757 0.2201 0.2814 0.3365 0.4092 0.5045 0.6051 0.7398 0.8798

0.1757 0.2201 0.2736 0.3376 0.4139 0.5042 0.6104 0.7347 0.8795

0.00 0.01 2.79 −0.34 −1.15 0.07 −0.87 0.69 0.04

263.15 268.15 273.15 278.15 283.15 288.15 293.15

0.2306 0.2796 0.3378 0.4027 0.4772 0.5703 0.6657

0.2308 0.2797 0.3368 0.4030 0.4793 0.5670 0.6670

−0.10 −0.05 0.31 −0.08 −0.45 0.58 −0.21

0.0807 0.1115 0.1406 0.1858 0.2623 0.3633 0.4763 0.6205 0.8311

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.0883 0.1193 0.1593 0.2106 0.2756 0.3573 0.4592 0.5852 0.7398

−9.45 −7.01 −3.71 −2.33 2.37 1.65 3.59 5.69 8.79

0.1218 0.1629 0.2173 0.2824 0.3746 0.4721 0.6008 0.7622 0.9689

12.36 9.34 6.65 2.81 −2.47 −3.13 −4.97 −8.07 −13.29

0.1327 0.1735 0.2248 0.2884 0.3668 0.4627 0.5790 0.7191 0.8868

4.51 3.44 3.42 0.74 −0.34 −1.07 −1.16 −1.96 −3.69

0.1577 0.2043 0.2642 0.3332 0.4280 0.5289 0.6540 0.8086 1.0005

10.26 7.18 6.12 0.97 −4.60 −4.84 −8.08 −9.29 −13.72

0.1710 0.2169 0.2728 0.3402 0.4210 0.5171 0.6308 0.7643 0.9203

2.70 1.45 3.06 −1.11 −2.89 −2.50 −4.25 −3.31 −4.60

0.2019 0.2533 0.3171 0.3876 0.4813 0.5829 0.6994

12.44 9.40 6.14 3.74 −0.86 −2.22 −5.07

0.2181 0.2680 0.3268 0.3957 0.4758 0.5686 0.6754

5.41 4.14 3.27 1.73 0.29 0.29 −1.46

ω1 = 0.2857

ω1 = 0.4445

ω1 = 0.6406

E



Article


x

cal

x

Jouyban−Acree model x

RD/%

cal

RD/%

Sun model x

cal

RD/%

ω1 = 0.6406 298.15 303.15

0.7802 0.9101

0.7808 0.9096

−0.08 0.06

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.2777 0.3291 0.3912 0.4561 0.5287 0.6138 0.7043 0.8188 0.9388

0.2778 0.3291 0.3877 0.4543 0.5298 0.6148 0.7103 0.8171 0.9361

0.00 0.00 0.90 0.39 −0.21 −0.17 −0.86 0.21 0.29

263.15 268.15 273.15 278.15 283.15 288.15 293.15 298.15 303.15

0.3245 0.3786 0.4412 0.5034 0.5796 0.6715 0.7536 0.8548 0.9657

0.3244 0.3786 0.4392 0.5069 0.5819 0.6648 0.7560 0.8560 0.9651

0.02 0.00 0.44 −0.69 −0.40 1.00 −0.32 −0.14 0.06

0.8419 1.0127

−7.91 −11.27

0.7975 0.9366

−2.22 −2.91

0.2515 0.3072 0.3745 0.4463 0.5389 0.6419 0.7514 0.8848 1.0400

9.45 6.64 4.27 2.15 −1.94 −4.58 −6.69 −8.05 −10.78

0.2707 0.3241 0.3853 0.4553 0.5349 0.6248 0.7261 0.8395 0.9659

2.54 1.51 1.51 0.17 −1.18 −1.79 −3.10 −2.52 −2.88

0.3245 0.3786 0.4412 0.5034 0.5796 0.6715 0.7536 0.8548 0.9657

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

0.3470 0.3972 0.4525 0.5131 0.5792 0.6511 0.7289 0.8130 0.9036

−6.94 −4.91 −2.56 −1.93 0.07 3.04 3.28 4.89 6.43

ω1 = 0.8261

ω1 = 1.0000

The standard uncertainties u are u(T) = 0.02 K, ur(p) = 0.05, ur(x) = 0.06, and ur(ω) = 0.05. ω is the mass-fraction composition of the mixed solvent. a

Figure 2. Experimental mole fraction solubility (x) (trifluoromethyl)pyridine with mole fraction in binary (ω1) + n-butanol(1 − ω1)) mixtures at different ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, □, ω1 = 0.8261; ○, ω1 = 1.0000.

of 2-chloro-3(ethyl acetatetemperatures: ω1 = 0.6406;

Figure 3. Experimental mole fraction solubility (x) of 2-chloro-3(trifluoromethyl)pyridine with mole fraction in binary (DMF(ω1) + n-butanol(1 − ω1)) mixtures at different temperatures: ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, ω1 = 0.6406; □, ω1 = 0.8261; ○, ω1 = 1.0000.

in binary solvent mixtures there was an increase with an increase in temperature, when the solvent composition was fixed. For the n-butyl alcohol + ethyl acetate binary solvent, at a given temperature, it increases monotonously with the rising mole fraction of ethyl acetate; for DMF + ethanol or DMF + n-butanol, at a given temperature, it increases monotonously with the rising mole fraction of DMF. This phenomenon may be caused by the strong

intermolecular interactions between the solute and the solvent molecules, which favor the dissolution of 2-chloro-3(trifluoromethyl)pyridine.23 In terms of the polarity of solvents, the polarity order of the experimental solvents is n-butyl alcohol > ethyl acetate. With the increasing of content of ethyl F



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Table 6. Modified Apelblat Parameters and RMSD Values for 2-Chloro-3-(trifluoromethyl)pyridine in Mixed Solvents of Ethyl Acetate(ω1) + n-Butanol(1 − ω1), DMF(ω1) + n-Butanol(1 − ω1), and DMF(ω1) + Ethanol(1 − ω1)a modified Apelblat ω1 0.0000 0.2857 0.4445 0.6406 0.8261 1.0000 0.0000 0.2857 0.4445 0.6406 0.8261 1.0000

Figure 4. Experimental mole fraction solubility (x) of 2-chloro-3(trifluoromethyl)pyridine with mole fraction in binary (DMF(ω1) + ethanol(1 − ω1)) mixtures at different temperatures: ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, ω1 = 0.6406; □, ω1 = 0.8261; ○, ω1 = 1.0000.

0.0000 0.2857 0.4445 0.6406 0.8261 1.0000

acetate, the polarity of mixed solvents decreases. So, with the decreasing of polarity, the solubility of 2-chloro-3-(trifluoromethyl)pyridine in mixed solvents increases. The polarity order of the experimental solvents is DMF > ethanol > n-butyl alcohol. With the increasing of the content of DMF, the polarity of mixed solvents (DMF + n-butanol, DMF + ethanol) increases. With the increasing of polarity, the solubility of 2-chloro-3(trifluoromethyl)pyridine in mixed solvents increases. 3.3. Solubility Modeling. 3.3.1. Modified Apelblat Equation. The modified Apelblat equation, which is a semiempirical equation with three parameters,10−15 is an accurate mathematical correlation for binary solid−liquid phase equilibrium. The modified Apelblat equation is B ln x = A + + C ln(T /K) (3) T where x and T respectively represent the measured solubility and studied temperature. A, B, and C are model parameters; the corresponding values are listed in Table 4. The correlated solubility values are presented in Tables 3, 4, and 5. The expression of relative deviation (RD) and the root-meansquare deviation (RMSD) are defined as follows: x − xical RD = i xi

RMSD = [

1 n

a

i=1

B

C

103 RMSD

ethyl acetate + n-butanol −2950.06 1.71179 −3443.58 −1.83780 −2027.20 1.94376 −2427.51 0.00420 −2192.92 0.01380 −1356.60 2.23998 DMF + n-butanol 7.99426 −3356.41 0.42112 8.15504 −2771.85 0.09468 7.58503 −2541.23 0.08029 7.52174 −2443.31 0.05659 6.12139 −2158.70 0.15465 8.81312 −2245.39 −0.25231 DMF + ethanol −3.22083 −3814.17 2.72796 14.8663 −3762.70 −0.45642 −3.90872 −2601.19 2.16317 −0.05891 −2353.42 1.35231 −4.43369 −1898.11 1.86008 8.81312 −2245.39 −0.25231 −0.72303 21.3558 −4.85836 7.64792 6.89692 −8.51993

2.65 13.92 12.69 10.04 6.77 12.63 2.41 2.86 5.49 51.96 7.55 1.83 3.23 8.53 16.82 1.70 13.35 1.83

Relative standard uncertainty ur(A) = ur(B) = ur(C) = 0.02.

3.3.2. Jouyban−Acree Model. The Jouyban−Acree model usually provides mathematic descriptions for the solubility dependence on both temperature and solvent composition for binary solvents.16−19 The model is described in eq 6: 2

ln x3 = ω1 ln x1 + ω2 ln x 2 +

ω1ω2 ∑ J (ω1 − ω2)i T i=0 i

(6)

In the above formula, x3 represents the mole fraction solubility of 2-chloro-3-(trifluoromethyl)pyridine in the binary solvent mixtures, x1 and x2 represent the mole fraction solubility of 2-chloro3-(trifluoromethyl)pyridine in pure solvent, ω1 and ω2 mean the mass fractions of solvent in binary solvent, respectively, and Ji represents parameter of the Jouyban−Acree model. 3.3.3. Sun Model. The Sun model is used to correlate the solubility data at different temperatures and different compositions of mixed solvents,20−22,25 which could be written as eq 7: ln x3 = D1 + D2 /T + D3ω1 + D4 ω1/T + D5ω12 /T + D6ω13/T + D7ω14 /T

(7)

where D1 to D7 are the model parameters Equations 6 and 7 can correlate the solubility of 2-chloro-3(trifluoromethyl)pyridine in mixed solvents of ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol, and the model parameters are listed in Table 5. The values of RMSD are also shown in Table 7. The solubility of 2-chloro-3(trifluoromethyl)pyridine in the binary solvents of ethyl acetate + n-butanol, DMF + n-butanol, and DMF + ethanol was calculated via the regressed parameters. In order to evaluate fitting results of the three models and measured solubility data, the corresponding values of RD and RMSD are listed in Tables 3−7 together with the evaluation

(4)

n

∑ (xical − xi)2 ]1/2

A

(5)

where n represents the number of experimental points, xi represents the experimental solubility of 2-chloro-3-(trifluoromethyl)pyridine, and xical is the calculated solubility. xical, along with RD, are listed in Tables 3, 4, and 5. The corresponding values of RMSD are listed in Table 6. The calculated values from the modified Apelblat equation are presented in Tables 3, 4, and 5. G



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Table 7. Parameters for Jouyban−Acree Model and Sun Model, RMSD Values for 2-Chloro-3(trifluoromethyl)pyridine in Mixed Solvents of (Ethyl Acetate + n-Butanol, DMF + n-Butanol, DMF + Ethanol)a Jouyban−Acree model ethyl acetate + n-butanol

103 RMSD DMF + n-butanol

103 RMSD DMF + ethanol

103 RMSD

J0 J1 J2

142.223 49.8814 286.069

J0 J1 J2

14.02 205.008 73.8141 450.865

J0 J1 J2

23.55 156.183 54.8661 280.164

38.12

Sun model D1 D2 D3 D4 D5 D6 D7 D1 D2 D3 D4 D5 D6 D7 D1 D2 D3 D4 D5 D6 D7

5.97251 −1878.7 4.0446 −996.98 −1423.3 2189.49 −1144.6 8.34 6.5454 −2007.4 3.37082 −639.17 −2239 3461.39 −1804.6 12.62 6.19474 −1908.7 7.48482 −1948.7 −1388.9 2122.87 −1114.9 20.54

Figure 5. Experimental mole fraction solubility (x) of 2-chloro-3(trifluoromethyl)pyridine with mole fraction in binary (ethyl acetate(ω1) + n-butanol(1 − ω1)) mixtures at different temperatures: ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, ω1 = 0.6406; □, ω1 = 0.8261; ○, ω1 = 1.0000. ―, calculated values from modified Apelblat equation.

a

Relative standard uncertainty ur(J0) = ur(J1) = ur(J2) = ur(D1) = ur(D2) = ur(D3) = ur(D4) = ur(D5) = ur(D6) = ur(D7) 0.02.

parameters. The values of RD and RMSD indicate that three models fit the solubility data quite well. In addition, the fitting parameters could provide an accurate prediction of the solubility data at any point within the experimental conditions. The maximum values of RMSD were 0.01392 (Apelblat), 0.01402 (Jouyban−Acree), and 0.00834 (Sun) in ethyl acetate + n-butanol, and for DMF + n-butanol, RMSDs were 0.05196 (Apelblat), 0.02355 (Jouyban−Acree), and 0.01262 (Sun), which indicates that the Sun model gives the best correlation of the solubility data in the binary ethyl acetate + n-butanol and DMF + n-butanol solvents. For DMF + ethanol, the maximum values of RMSD were 0.01682 (Apelblat), 0.03812 (Jouyban−Acree), and 0.02054 (Sun), which indicates that the Apelblat model gives the best correlation of the solubility data in the binary DMF + ethanol solvent. In order to show the obvious relation between temperature and the solubility of 2-chloro-3-(trifluoromethyl)pyridine in three binary solvents and the fitting results by modified Apelblat equation, the calculated values from the modified Apelblat equation are presented in Figures 5, 6, and 7.

Figure 6. Experimental mole fraction solubility (x) of 2-chloro-3(trifluoromethyl)pyridine with mole fraction in binary (DMF(ω1) + n-butanol(1 − ω1)) mixtures at different temperatures: ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, ω1 = 0.6406; □, ω1 = 0.8261; ○, ω1 = 1.0000. ―, calculated values from modified Apelblat equation.

acetate. With the increasing of the content of ethyl acetate, the polarity of mixed solvents decreases. So, with the decreasing of polarity, the solubility of 2-chloro-3-(trifluoromethyl)pyridine in mixed solvents increases. The polarity order of the experimental solvents is DMF > ethanol > n-butyl alcohol. With the increasing of the content of DMF, the polarity of mixed solvents increases. With the increasing of polarity, the solubility of 2-chloro-3-(trifluoromethyl)pyridine in mixed solvents increases. The experimental solubility data were correlated via using three models. The RD and RMSD values of every model were less than 0.147 and 0.051, respectively. Accordingly, the modified Apelblat model, Jouyban−Acree model, and Sun model were used to correlate the obtained experimental solubility data. The values

4. CONCLUSIONS In this paper, the solubility of 2-chloro-3-(trifluoromethyl)pyridine in binary (ethyl acetate + n-butanol, DMF + n-butanol, DMF + ethanol) solvent mixtures was measured experimentally at temperatures ranging from 263.15 to 303.15 K under atmospheric pressure. The solubility of 2-chloro-3-(trifluoromethyl)pyridine in binary solvent mixtures increased with increasing temperature. In terms of the polarity of solvents, the polarity order of the experimental solvents is n-butyl alcohol > ethyl H



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Figure 7. Experimental mole fraction solubility (x) of 2-chloro-3(trifluoromethyl)pyridine with mole fraction in binary (DMF(ω1) + ethanol(1 − ω1)) mixtures at different temperatures: ■, ω1 = 0; ●, ω1 = 0.2857; ★, ω1 = 0.4445; ☆, ω1 = 0.6406; □, ω1 = 0.8261; ○, ω1 = 1.0000. ―, calculated values from modified Apelblat equation.

of RMSD indicate that the Sun model gave the best correlation of the solubility data in the binary ethyl acetate + n-butanol and DMF + n-butanol solvents; the Apelblat model gave the best correlation of the solubility data in the binary DMF + ethanol solvent. In addition, the obtained parameters could provide a prediction of the solubility data at any point under the experimental conditions.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Li Xu: 0000-0001-9083-4858 Notes

The authors declare no competing financial interest.

■ ■

ACKNOWLEDGMENTS We would like to acknowledge the editors and reviewers. Thank you for your valuable advice. REFERENCES

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Solubility Behavior of 2-Chloro-3- (trifluoromethyl)pyridine in (Ethyl

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