Solubility of Diflufenican in Pure and Binary Solvent Systems - Journal

Oct 17, 2018 - Two binary solvent systems (acetone + water, acetone + ethanol) were ... The solubility data were well correlated by the modified Apelb...
0 downloads 0 Views 2MB Size
Download PDF
Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

pubs.acs.org/jced

Solubility of Diflufenican in Pure and Binary Solvent Systems Liangcheng Song,†,‡ Danyang Zhao,† Shuguang Zhang,∥ Xiao Zhang,† Guan Wang,† Chongqiang Zhu,† Yu Tian,‡,§ and Chunhui Yang*,†,§ †

School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, People’s Republic of China School of Environment, Harbin Institute of Technology, Harbin 150090, People’s Republic of China § State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (SKLUWRE, HIT), Harbin 150090, People’s Republic of China ∥ Nantong Jiahe Chemicals Co., Ltd., Haimen 226100, People’s Republic of China Downloaded via UNIV OF WINNIPEG on October 17, 2018 at 21:16:25 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

‡

ABSTRACT: With the aid of a laser monitoring technique, the solution thermodynamics of diflufenican was sysmatically studied in the pure and binary solvent systems. The solubility screening results showed that diflufenican had excellent solubility in ethyl acetate, acetone, benzene, and toluene which could be used as good solvents. While methanol, ethanol, isopropyl alcohol and cyclohexane were the poor solvents for diflufenican as the solubility was quite small. Two binary solvent systems (acetone + water, acetone + ethanol) were composed, which exhibited a wide solubility range of diflufenican. The solubility data were well correlated by the modified Apelblat model, NRTL model, van’t Hoff model, λh model, and Jouyban−Acree model, which provided the basis for the design and optimization for the diflufenican crystallization process.

1. INTRODUCTION Diflufenican (CAS No.83164-33-4, shown in Figure 1) is one of the amide herbicides, whose IUPAC name is

2-(3-trifluoromethylphenoxy)-3-pyridinecarboxylic acid was acquired by a chloridization reaction.6 The purity of the crystallized diflufenican obtained from the mixture of toluene and hexane is only 97%.11 To further improve the purity of diflufenican, a great number of solvents were screened in this work. The solubility of diflufenican in pure and binary solvents was exactly measured, and the data were well correlated with different models.

2. EXPERIMENTAL SECTION 2.1. Materials. The white crystalline solid of diflufenican (mass fraction purity ≥ 99.3%) was obtained from Nantong Jiahe Chemicals Co., Ltd., China. The organic solvents were of analytical grade in this work, and directly used without any further purification. The water used in this work was deionized water with conductivity below 2 μS·cm−1. More detailed information about the materials was listed in Table 1. 2.2. Solubility Measurement. The solubility of diflufenican in pure solvents (methanol, ethanol, isopropyl alcohol, ethyl acetate, acetone, toluene, cyclohexane, and benzene) and binary solvents (acetone + water, acetone + ethanol) was determined by a dynamic method using the laser detecting technique, whose accuracy has been confirmed in previous literature.12−14 The experimental device, same as that in previous literature, is shown in Figure 2.15 The measurement was carried out in a

Figure 1. Molecular structure of diflufenican.

N-(2,4-difluorophenyl)-2-(3-trifluoromethylphenoxy)-3-pyridinecarboxamide.1 It is a selective pre- and early postemergence herbicide used for protecting winter cereals,2,3 especially wheat and barley. Diflufenican was first synthesized by May & Baker Limited (now in Bayer Group) in 1982.4 It is usually applied to the soil,5 or on the apical meristem compounded with isoproturon and chlortoluron6,7 in order to promote the absorption of the active ingredient. The weeding mode of diflufenican is to stop the photosynthesis of the weeds. It inhibits the biosynthesis of phytoene desaturase8,9 without which carotenoids cannot be synthesized.9 For the lack of its raw material carotenoids, consequently, photosynthesis will not proceed.10 Because of its high selectivity, diflufenican is now globally adopted to control broad-leaved grasses,7 including Galium aparine, Veronica hederifolia, Veronica persica, and Viola arvensis.6 In industry, diflufenican was synthesized through the substitution reaction between 2,4-difluoroaniline and 2-(3-trifluoromethylphenoxy)-3-pyridinecarboxylic acid chloride, in which © XXXX American Chemical Society

Received: July 20, 2018 Accepted: October 2, 2018

A

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Materials Used in This Work chemical name diflufenican ethanol benzene acetone toluene ethyl acetate cyclohexane methanol isopropyl alcohol KNO3 water

source Nantong Jiahe Chemicals Co., Ltd., China Kemiou Chemical Reagent Co., Ltd. China Kemiou Chemical Reagent Co., Ltd. China Bohai Chemical Technology Co., Ltd. China Bohai Chemical Technology Co., Ltd. China Xilong Chemical Reagent Co., Ltd. China Xilong Chemical Reagent Co., Ltd. China Xilong Chemical Reagent Co., Ltd. China Xilong Chemical Reagent Co., Ltd. China Xilong Chemical Reagent Co., Ltd. China our lab

mass fraction purity

analysis method

99.3%

HPLCa

99.8%

GCb

99.8%

GCb

99.5%

GCb

99.5%

GCb

99.7%

GCb

99.7%

GCb

99.5%

GCb

99.7%

GCb

99.0%

GCb

>99.9%

GCb

Table 2. Comparisons between the Experimental Solubility (xexp KNO3) of KNO3 in Water at 101.3 kPa and the Data from a Literature (xlit KNO3) T/K

10xexp KNO3

10xlit KNO3

100RD

283.15 293.15 303.15 313.15

0.3507 0.5340 0.7549 1.043

0.3427 0.5260 0.7364 1.077

2.334 1.521 2.512 −3.157

a exp xKNO3

and xlit KNO3 represent the experimental mole fraction solubility of KNO3 and literature data, respectively. RD is the relative deviation between the experimental data and the literature data. Standard uncertainty of temperature and pressure are u(T) = 0.05 K, u(P) = 0.012 MPa. Relative standard uncertainty of mole fraction solubility is ur(xexp KNO3) = 0.03.

solute dissolved) could not be dissolved in 60 min, which indicated that the solution was saturated. Each data point was measured at least three times to ensure the accuracy. The mole fraction solubility value was calculated according to eq 1. x1 =

a

High-performance liquid chromatography. bGas chromatography.

md /Md md /Md + ms /Ms

(1)

where md and ms represent the mass of diflufenican and solvent, respectively. Md and Ms are the respective molecular masses. For binary solvent systems, the composition is expressed by the mole fraction of sSolvent 1 calculated according to eq 2.

jacketed glass crystallizer, whose interlayer was connected with a water bath (SHP DC-2015, China) to control the temperature. The solution inside the crystallizer was stirred by a magnetic stirrer (D2004W), and its temperature was precisely measured by a mercury thermometer (standard uncertainty, 0.05 K). A condenser was equipped with the crystallizer to prevent solvent losses. The dissolution process of diflufenican was monitored by the laser detecting system. All the chemicals were weighed by an electronic balance (Toledo AB204-S, Switzerland) with uncertainty of ±0.0002 g. In the experiment, a predetermined amount of solvent was delivered to the crystallizer and stirred at the required temperature. When the system reached the thermal equilibrium, a certain quality of diflufenican was added to the crystallizer. The laser intensity decreased instantaneously as the laser beam was obstructed by the solid particles. The laser intensity gradually increased as the particles began to dissolve, and it restored to the maximum when the particles were completely dissolved. Then diflufenican was added again. The additions continued until an addition of 2 to 4 mg (less than 1% of the mass of

xs1 =

ms1/Ms1 ms1/Ms1 + ms2 /Ms2

(2)

where ms1 and ms2 represent the mass of solvent 1 and solvent 2 in the binary solvent mixture. Ms1 and Ms2 are the respective molecular masses. 2.3. Thermal Analysis. A compound may have different solubilities due to its polymorphs, so it is necessary to claim the crystal form when the solubility is discussed. In this work, the crystal form of the equilibrium solid phase was identified by X-ray powder diffraction (Bruker D8; Cu Kα radiation, 0.15418 nm), and all the samples were scanned from 5° to 60° with a rate of 6°·min−1. Differential scanning calorimetry (DSC 1/500, MettlerToledo, Swizerland) was used to obtain the melting temperature (Tm) and the enthalpy of fusion (ΔfusH) of diflufenican.

Figure 2. Experimental device for solubility measurement: (1) water bath; (2) laser generator; (3) laser receiver; (4) signal display; (5) magnetic stirrer; (6) jacketed glass crystallizer; (7) condenser-Allihn type; (8) mercury thermometer. B

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

The instrument was standardized using indium as a reference material prior to the experimentation. Approximate 9.5 mg of sample was heated at a rate of 5 K·min−1 from 373.15 K to 523.15 K under the protection of nitrogen. The standard uncertainties for temperature and enthalpy of fusion were 0.25 K and 0.250 kJ·mol−1, respectively. 2.4. Verification of the Experimental Method. To verify the accuracy of the experimental method, the solubility of KNO3 in water was measured by the laser dynamic method used in this work. The obtained experimental data were compared with the data from literature,16 presented in Table 2, from which it can be seen that the solubility measured in this work is basically consistent with the data from the literature. Consequently, the laser dynamic method is reliable and fit for the solubility measurement of diflufenican in this work.

3. THERMODYNAMIC MODELS 3.1. The Modified Apelblat Model. The modified Apelblat model, a semiempirical model, is derived from eq 3 which is established based on the relationship of the solute fugacity in the solid phase and liquid phase at equilibrium and then deduced with the help of Clausiuse−Clapeyron equation.17,18 −ln x1 =

Figure 3. X-ray diffraction patterns of the solid phase from the saturated solutions and the raw material: (A) ethanol; (B) ethyl acetate; (C) acetone; (D) benzene; (E) toluene; (F) cyclohexane; (G) methanol; (H) isopropyl alcohol; (I) acetone + water; (J) acetone + ethanol; (K) raw material.

yz ΔfusH ijj 1 T 1 yzz ΔCpf ijj T + m − 1zzz jjj − zzz − jjjln z R kT Tm { R k Tm T {

+ ln γ1

(3)

where Tm, ΔCpf, ΔfusH, and γ1 refer to the melting temperature of solute, the difference of heat capacity of solute between being in the solid state and being in the liquid state, the melting enthalpy and activity coefficient, respectively, while T is the temperature of phase equilibrium. In a short temperature range, the activity coefficient can be calculated according to an empirical equation, eq 4.19 ln γ1 = α +

β T

(4)

where α and β are the empirical parameters. Substituting eq 4 into eq 3, the solubility can be expressed as a function of temperature through eq 5, which is further simplified conveniently as eq 6, the modified Apelblat model. ÄÅ ÉÑ ÅÅ Δ H ÑÑ ΔC pf fus Å Å ln x1 = ÅÅ − (1 + ln Tm) − α ÑÑÑÑ ÅÅ RTm ÑÑÑ R Ç Ö É ÅÄÅi ΔC Ñ Ñ ΔC pf y ÑÑ 1 Δ Hz pf ÅÅj + ÅÅÅjjj − fus zzzTm − β ÑÑÑ + ln T j z ÅÅ R ÑÑ T RTm { R ÅÇk ÑÖ

ln x1 = A +

B + C ln T T

ln γ1 = (5) (6)

where A, B, and C are adjustable parameters. 3.2. The NRTL Model. The NRTL model is a further simplication of eq 3 when the difference of heat capacity (ΔCpf) of solute between being in the solid state and being in the liquid state is negligible, which is presented as eq 7.20 ln x1 =

ΔfusH ijj 1 1 yz − zzz − ln γ1 jjj R k Tm T z{

ÄÅ Åi

É yzÑÑÑÑ z zzÑÑÑ + x 2 + G12x12 z{ÑÑÑÖ

Figure 4. DSC curve of diflufenican.

ÅÅj x 22ÅÅÅjjj Åj

2 τ21G21

ÅÅÇk x1 + G21x 2 2

2 τ12G12

(8)

G12 = exp( −α12τ12)

(9)

G21 = exp( −α12τ21)

(10)

τ12 =

τ21 =

g12 − g22 RT

g21 − g11 RT

=

Δg12

=

Δg21

RT

RT

(11)

(12)

where g21 is equal to g12; Δg12 and Δg21, the adjustable parameters, are relevant to the cross interaction energy; x2 is the mole fraction of the solvent; α12 denotes the nonrandomness of the mixture and it generally ranges from 0 to 1. 3.3. The van’t Hoff Model. The van’t Hoff model is derived from eq 7 on the condition of a dilute solution which is approximately considered as an ideal solution. The equation

(7)

The activity is considered in the equation for a real solution, and the activity coefficient (γ1) of solute in pure solvent can be calculated according to the NRTL model by the following equations.21,22 C

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 3. Experimental and Calculated Solubility Values of Diflufenican in Eight Pure Solvents Ranging from (278.15 to 323.15) K at 101.3 kPaa T/K

104xexp 1

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

2.507 3.317 4.299 5.446 6.807 8.574 10.69 13.86 17.31 21.35

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

107.4 125.6 147. 9 172.8 202.4 236.7 272.2 314.1 366.1 423.4

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

90.26 107.4 127.4 152.0 180.0 210.5 246.7 290.3 338.8 408.5

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

51.26 63.77 77.90 95.36 116.0 141.7 177.3 214.7 252.2 302.8

104xcal,vH 1

104xcal,λh 1

Ethanol 2.496 2.420 3.268 3.181 4.240 4.144 5.451 5.352 6.951 6.856 8.792 8.717 11.04 11.00 13.75 13.80 17.02 17.20 20.92 21.32 Ethyl Acetate 105.5 105.0 125.5 124.7 148.4 147.4 174.5 173.3 204.1 202.8 237.5 236.3 275.0 274.3 316.9 317.3 363.6 365.9 415.4 420.6 Acetone 88.75 86.58 107.2 104.8 128.7 126.1 153.6 150.9 182.2 179.6 214.8 212.6 252.0 250.6 294.1 294.1 341.6 343.8 394.9 400.3 Toluene 50.25 49.82 63.03 62.52 78.45 77.86 96.90 96.29 118.9 118.3 144.8 144.4 175.3 175.2 210.9 211.4 252.3 253.7 300.1 303.1

104xcal,Apel 1

104xcal,NRTL 1

T/K

104xexp 1

2.549 3.287 4.219 5.390 6.853 8.674 10.93 13.72 17.15 21.36

2.585 3.252 4.136 5.347 6.933 8.779 11.15 13.40 16.86 21.33

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

1.034 1.620 2.287 3.341 4.584 6.134 8.063 11.18 14.74

107.2 126.1 147.9 173.0 201.9 235.0 273.0 316.4 365.9 422.3

107.2 126.1 147.9 173.1 201.9 235.0 273.1 316.4 365.4 421.2

90.53 107.5 127.5 150.9 178.4 210.6 248.2 292.1 343.2 402.7

89.05 106.7 127.3 151.5 179.6 212.3 250.2 293.8 344.1 401.2

51.17 63.36 78.13 95.96 117.4 143.1 173.9 210.5 254.0 305.5

50.55 63.00 78.09 96.27 118.1 144.0 174.8 211.2 254.3 304.6

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

59.89 78.03 96.45 118.0 144.7 175.2 215.4 262.9 319.4

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

2.353 2.932 3.772 4.735 6.004 7.499 9.377 11.74 14.75 18.73

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.4652 0.7358 1.162 1.827 2.818 4.314 6.655 10.00 15.19 22.00

104xcal,vH 1

104xcal,λh 1

Cyclohexane 1.101 1.150 1.589 1.643 2.263 2.320 3.185 3.238 4.433 4.470 6.103 6.109 8.319 8.268 11.23 11.09 15.02 14.74 Benzene 60.63 59.91 76.38 75.59 95.46 94.65 118.4 117.7 145.9 145.2 178.5 178.1 216.9 217.2 262.1 263.2 314.8 317.3 Methanol 2.257 2.125 2.934 2.788 3.779 3.624 4.827 4.672 6.114 5.974 7.684 7.583 9.586 9.557 11.88 11.97 14.61 14.89 17.86 18.43 Isopropyl Alcohol 0.4474 0.4183 0.7313 0.6916 1.175 1.124 1.858 1.796 2.892 2.826 4.438 4.380 6.715 6.692 10.03 10.09 14.79 15.01 21.54 22.06

104xcal,Apel 1

104xcal,NRTL 1

1.061 1.577 2.292 3.262 4.553 6.236 8.391 11.10 14.46

1.083 1.571 2.249 3.180 4.442 6.134 8.380 11.34 15.19

61.05 76.48 95.23 117.9 145.1 177.7 216.6 262.6 316.9

61.00 76.50 95.36 118.1 145.5 178.1 216.7 262.3 315.9

2.347 2.966 3.746 4.725 5.954 7.494 9.420 11.83 14.83 18.57

2.352 2.931 3.773 4.734 6.004 7.498 9.376 11.73 14.74 18.74

0.4629 0.7383 1.166 1.824 2.826 4.342 6.613 9.991 14.98 22.28

0.4400 0.7367 1.201 1.909 2.969 4.527 6.781 9.997 14.55 20.90

a exp x1 represents the experimental mole fraction solubility; xcal,vH , xcal,λh , xcal,Apel , and xcal,NRTL represent the calculated solubility of diflufenican by 1 1 1 1 using van’t Hoff model, λh model, modified Apelblat model, and NRTL model, respectively. Standard uncertainty of temperature and pressure are u(T) = 0.05 K, u(P) = 0.012 MPa. Relative standard uncertainty of mole fraction solubility is ur(x0) = 0.03.

evaluated by the vapor pressure of solvent in the saturated solution through experiments, and then the equation can be used to correlate the solubility curves of nonideal solutions, presented as eq 15. ÅÄÅ ÑÉ i1 λ(1 − x1) ÑÑÑ Å 1 yzz ÑÑ = λhjjjj − lnÅÅÅÅ1 + z Ñ jT ÅÅÇ ÑÑÖ x1 Tm zz{ (15) k

turns to a function of temperature as eq 13 when the activity coefficient equals 1 in the ideal solution, simplified as eq 14:23 ln x1 =

ΔfusH Δ H 1 − fus RTm R T

ln x1 = a +

b T

(13)

(14)

where a and b are equation parameters. 3.4. The λh Model. The λh model was proposed by Buchowski et al. in 1980.24 It is a modification of the explicit formula for ideal solubility, in which the activity of solute is

where λ and h are the equation parameters. The value of h is the solution enthalpy per mole of solute divided by the gas constant, and λ indicates the nonideal degree of the saturated D

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

3.5. The Jouyban−Acree Model. The Jouyban−Acree model, a mathematical representation of experimental solute solubilities in binary solvent mixtures, was based on the twobody and three-body interactional mixing rule, in which molecule interactions were taken into account.25 As shown in eq 16, the model describes that solubility is a function of solvent composition and temperature.26 ln x1 = xs1 ln(x1)s1 + xs2 ln(x1)s2 +

xs1xs2 T

2

∑ Ji (xs1 − xs2)i 0

(16)

where Ji is the model parameter and T is the temperature of phase equilibrium. xs1 and xs2 refer to the mole fraction of solvent 1 and solvent 2 in the binary solvent mixture. (x1)s1 and (x1)s2 represent the solubility of solute in the pure solvent 1 and solvent 2, respectively, which can be calculated from the van’t Hoff equation, shown as eq 17 and eq 18.

Figure 5. Solubility of diflufenican in eight solvents at different temperatures: ■, ethanol, black; ●, ethyl acetate, red; ▲, acetone, blue; ▼, toluene, pink; ⧫, cyclohexane, green; ◀, benzene, purple; ▶, methanol, violet; ★, isopropyl alcohol, dark yellow.

solution. Both the parameters can be regressed from the experimental solubility data.

ln(x1)s1 = a1 +

b1 T

(17)

ln(x1)s2 = a 2 +

b2 T

(18)

Table 4. Experimental Solubility (104x1) of Diflufenican and Calculated Values (104xcal 1 ) by Jouyban−Acree Model in Binary Acetone (s1) + Water (s2) and Acetone (s1) + Ethanol (s3) Solvent Systems Ranging from (278.15 to 323.15) K at 101.3 kPaa,b T/K

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

104x1 Acetone (s1) xs1 = 56.82 71.02 86.48 103.6 124.5 153.2 187.0 223.8 263.0 304.5 xs1 = 36.77 45.97 56.73 70.98 87.79 109.1 130.5 158.9 194.5 230.1 xs1 = 23.27 29.63 37.36 46.87 58.22 71.93 88.20 107.4 130.3 156.5

104xcal 1 + Water(s2) 0.90 57.44 70.90 86.88 105.7 127.8 153.6 183.4 217.8 257.2 302.2 0.80 37.26 46.79 58.30 72.08 88.50 107.9 130.7 157.5 188.5 224.5 0.70 22.85 29.22 37.04 46.58 58.14 72.02 88.61 108.3 131.5 158.8

T/K

100RD

104x1

104xcal 1

100RD

11.84 15.46 20.01 25.66 32.64 41.19 51.58 64.14 79.21 97.18

−3.030 −0.9609 −1.185 1.103 −0.3663 0 1.316 1.263 1.408 2.048

xs1 = 0.60 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

1.091 −0.1690 0.4625 2.027 2.651 0.2611 −1.925 −2.681 −2.205 −0.7553

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

1.333 1.784 2.767 1.550 0.8087 −1.100 0.1533 −0.8811 −3.085 −2.434 −1.805 −1.384 −0.8565 −0.6187 −0.1374 0.1251 0.4649 0.8380 0.9210 1.470

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 E

12.21 15.61 20.25 25.38 32.76 41.19 50.91 63.34 78.11 95.23

xs1 = 0.50 4.334 4.330 5.760 5.770 7.603 7.670 9.966 10.09 12.69 13.15 16.82 17.00 21.89 21.78 27.92 27.70 36.04 34.95 44.74 43.79 Acetone (s1) + Ethanol (s3) xs1 = 0.90 78.82 76.75 94.53 92.97 112.2 111.9 132.9 133.8 157.2 159.0 185.5 187.9 219.3 220.9 259.7 258.3 303.3 300.5 351.6 348.0

−0.09229 0.1736 0.8812 1.244 3.625 1.070 −0.5025 −0.7880 −3.024 −2.123

−2.626 −1.650 −0.2674 0.6772 1.145 1.294 0.7296 −0.5391 −0.9232 −1.024

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 4. continued T/K

104x1

104xcal 1

104x1

T/K

100RD

xs1 = 0.80 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

65.97 80.71 97.26 114.4 137.3 162.0 188.9 223.2 259.3 302.5

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

53.12 65.57 79.42 94.40 112.2 133.6 159.3 189.5 225.4 266.8

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

41.59 50.95 61.87 75.80 91.34 109.7 131.7 157.6 187.9 224.4

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

32.81 40.45 49.86 60.00 71.19 85.49 103.8 125.9 151.5 180.6

104xcal 1

100RD

22.97 28.66 35.49 43.62 53.24 64.57 77.81 93.21 111.0 131.5

0.04355 −0.3477 −0.6161 1.726 0.8524 1.493 0.9995 2.632 1.463 −0.07599

15.31 19.27 24.06 29.82 36.68 44.83 54.42 65.67 78.77 93.95

−0.4551 −1.834 −1.232 −1.421 −0.6501 −0.4883 −0.4573 0.5512 −0.1395 0.1492

9.352 11.89 15.00 18.77 23.31 28.74 35.20 42.84 51.80 62.28

−0.7956 −2.220 −0.6623 −1.002 −0.4272 −0.2430 0.2563 1.661 1.132 −0.3679

5.152 6.633 8.465 10.71 13.45 16.76 20.74 25.49 31.13 37.77

−1.246 0.9589 0.6181 1.709 1.740 2.508 2.521 1.111 −0.6066 −0.8661

xs1 = 0.40 64.80 78.86 95.32 114.5 136.6 162.1 191.3 224.5 262.2 304.8

−1.774 −2.292 −1.995 0.08741 −0.5098 0.06173 1.271 0.5824 1.118 0.7603

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

22.96 28.76 35.71 42.88 52.79 63.62 77.04 90.82 109.4 131.6

53.30 65.20 79.19 95.55 114.6 136.6 161.8 190.8 223.7 261.0

0.3389 −0.5643 −0.2896 1.218 2.139 2.246 1.569 0.6860 −0.7542 −2.174

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

15.38 19.63 24.36 30.25 36.92 45.05 54.67 65.31 78.88 93.81

42.32 52.07 63.59 77.14 92.97 111.4 132.6 157.1 185.0 216.8

1.755 2.198 2.780 1.768 1.785 1.550 0.6834 −0.3173 −1.543 −3.387

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

9.427 12.16 15.10 18.96 23.41 28.81 35.11 42.14 51.22 62.51

32.10 39.75 48.85 59.63 72.29 87.08 104.3 124.2 147.0 173.1

−2.164 −1.731 −2.026 −0.6167 1.545 1.860 0.4817 −1.350 −2.970 −4.153

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

5.217 6.570 8.413 10.53 13.22 16.35 20.23 25.21 31.32 38.10

xs1 = 0.70

xs1 = 0.30

xs1 = 0.60

xs1 = 0.20

xs1 = 0.50

xs1 = 0.10

a

x1, xs1 and xcal 1 represent the experimental solubility, the solute-free mole fraction of acetone and calculated mole fraction solubility, respectively; Standard uncertainty of temperature and pressure are u(T) = 0.05 K, u(P) = 0.012 MPa. Relative standard uncertainty of solvent composition and mole-fraction solubility are ur(xs1) = 0.0004, ur(x0) = 0.03. b

By substituting eq 17 and eq 18 into eq 16, the Jouyban−Acree model is reformed as eq 19.26 x A ln x1 = A1 + 2 + A3xs1 + A4 s1 T T xs12 xs13 x4 + A5 + A6 + A 7 s1 (19) T T T where A1 to A7 are the model parameters. To evaluate the correlation models, the relative deviation (RD), the average relative deviation (ARD), and the rootmean-square deviation (RMSD) are defined as eq 20, eq 21, and eq 22, respectively.

RD =

x1cal − x1exp x1exp

ARD =

100 N

N

∑

(20)

x1cal − x1exp x1exp

ÄÅ N É ÅÅ ∑ (x cal − x exp)2 ÑÑÑ1/2 ÅÅ i = 1 1 ÑÑ 1 ÑÑ RMSD = ÅÅÅ ÑÑ ÅÅ N ÑÑÖ ÅÇ

xexp 1

i=1

(21)

(22)

xcal 1

where is the experimental solubility and is the calculated solubility according to the correlation models. F

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Figure 6. Solubility of diflufenican in binary solvent systems: (a) acetone + water; (b) acetone + ethanol.

Table 5. Parameters A, B, and C of modified Apelblat model for the solubility of diflufenican in pure solvents

4. RESULTS AND DISCUSSION 4.1. Thermal Analysis Results. The XRD patterns of diflufenican in the selected solvents and the raw material are presented in Figure 3. The XRD patterns of the equilibrium solid phase in all the solvents have the same characteristic peaks with the raw material, which indicates that the crystal structure of diflufenican remains unchanged during the solubility measurements. The DSC curve of diflufenican is shown in Figure 4. It can be seen that only one endothermic peak appears in the curve, which represents the melting process of diflufenican. The maximum point of the curve is the melting temperature (Tm), which can be determined as 435.52 ± 0.25 K. The melting enthalpy is 39.421 ± 0.250 kJ·mol−1. The data are necessary for the solubility correlation and the calculation of the activity coefficient in the NRTL model and the λh model. 4.2. Solubility Data of Diflufenican. The solubility data of diflufenican in eight pure solvents (acetone, methanol, ethanol, isopropyl alcohol, cyclohexane, ethyl acetate, toluene. and benzene) are listed in Table 3 and graphically presented in Figure 5. The solubility of diflufenican increases with the increasing temperature in each solvent. At a fixed temperature, the solubility in the studied pure solvents ranks as ethyl acetate > acetone > toluene ≈ benzene > ethanol > methanol > isopropyl alcohol ≈ cyclohexane. It can be easily seen from Figure 5 that the solubility curves can be divided into two categories. Some increase obviously with the temperature in the picture while the others do not. The detailed experimental data shows that the solubilities in ethyl acetate, acetone, toluene, and benzene are quite larger than those in methanol, ethanol, isopropyl alcohol, and cyclohexane, and at least 15 times of those at the same temperature, which illustrates that ethyl acetate, acetone, toluene, and benzene are good solvents for diflufenican while methanol, ethanol, isopropyl alcohol, and cyclohexane are the poor ones that can be used as antisolvent. It has been proven that solubility can be influenced by the polarity of solvents,27,28 the ability to form hydrogen bonds between solute and solvent,29 the π−π conjugate,30 the size of molecular, the steric effects,31 and so on. From Figure 1, it can be found that there are two benzene rings in the molecule of diflufenican, which easily forms the π−π conjugate with aromatic solvents. The formation of π−π conjugate between the solute and the solvent promotes dissolution, so it results that diflufenican is soluble in benzene and toluene. On the other hand, the amide group from diflufenican can work as a hydrogen donor which makes diflufenican soluble in acetone and ester due to the formation of

solvent

A

B

C

ARD

104RMSD

ethanol benzene ethyl acetate cyclohexane acetone toluene methanol isopropyl alcohol

−76.91 −28.01 −60.81 210.3 −90.86 −64.85 −149.7 −118.2

−498.4 −2137 215.6 −14900 1346 −334.8 2846 −1660

12.51 5.395 9.860 −29.54 14.45 10.80 23.30 20.29

1.154 0.9367 0.3006 1.875 0.6077 0.9417 0.5836 0.5652

0.1128 1.470 1.032 0.1537 2.497 2.103 0.06815 0.1119

Table 6. Parameters Δg12, Δg21 and α1 of NRTL Model for the Solubility of Diflufenican in Pure Solvents solvent ethanol benzene ethyl acetate cyclohexane acetone toluene methanol isopropyl alcohol

10−2Δg12 10−2Δg21 24.15 468.3 1274 −1340 4014 2742 3631 12.46

−122.8 −413.8 −1163 1383 −3923 −2676 −3459 −6.480

102α1

ARD

104RMSD

0.4169 0.8472 0.2265 0.04551 0.01816 0.02705 0.02160 0.7912

2.524 1.018 0.3497 2.862 0.9453 1.169 1.468 3.482

0.2703 1.768 1.223 0.2057 3.339 1.945 0.1786 0.4138

hydrogen binding with the carbonyl oxygen in the solvent molecules. The solubility of diflufenican in the binary solvent systems (acetone + water, acetone + ethanol) was measured during the temperature range from 278.15 K to 323.15 K. The experimental data are listed in Table 4 and plotted as 3D drawings in Figure 6. The figures show that in each binary solvent system the solubility of diflufenican increases apparently with the temperature when the solvent composition is fixed, while at a given temperature it increases monotonously with the rising mole fraction of acetone. From the comparison of the two solubility surfaces in the 3D drawings, it can be found that the solubility decreases much faster with the decreasing mole fraction of acetone in the binary acetone + water solvent system. This is attributed to one of the components, water, in which diflufenican is practically insoluble. The solubility of diflufenican in the binary acetone + water solvent mixture ranges from 4.334 × 10−4 to 408.5 × 10−4, and the minimum is only about 1% of the maximum. Such a large solubility range indicates that the binary acetone + water solvent system is fit for the dilution crystallization of diflufenican. Compared with ethanol, water can be employed as a better antisolvent for a higher yield.26,32 G

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

that all the models fit the solubility data quite well, among which the modified Apelblat model gives the best correlation of the solubility data in the pure solvents. For the binary solvent systems, the Jouyban−Acree model presents the solubility data as a function of both solvent composition and temperature, which generates the solubility surfaces as Figure 7. The ARD values for the acetone + water and acetone + ethanol solvent systems are 1.365% and 1.308%, respectively, which demonstrates the Jouyban−Acree model with the obtained parameters in Table 8 can provide an accurate prediction of the solubility data at any point within the experimental condition.

Table 7. Parameters a and b of van’t Hoff Model for the Solubility of Diflufenican in Pure Solvents solvent

a

b

ARD

104RMSD

ethanol benzene ethyl acetate cyclohexane acetone toluene methanol isopropyl alcohol

6.974 8.201 5.292 11.99 5.995 7.540 6.461 17.81

−4247 −3767 −2738 −5976 −2981 −3569 −4132 −7738

1.580 1.097 0.8841 2.604 1.481 1.397 1.959 1.868

0.2186 2.129 3.102 0.1493 5.150 2.191 0.3006 0.1996

Table 8. Parameters λ and h of λh Model for the Solubility of Diflufenican in Pure Solvents solvent

λ

h

ARD

104RMSD

ethanol benzene ethyl acetate cyclohexane acetone toluene methanol isopropyl alcohol

0.06359 0.6375 0.3184 0.1522 0.4049 0.5041 0.05351 1.233

67490 5930 8301 38220 7334 7058 79590 6427

1.940 0.9877 0.6451 2.601 1.583 1.310 2.791 2.578

0.1395 1.689 1.730 0.09968 3.869 1.863 0.1736 0.07513

5. CONCLUSION Solubility of diflufenican in eight pure solvents and two binary solvent systems was accurately measured from 278.15 to 323.15 K by using laser monitoring technique. The solubility of diflufenican increased with increasing temperature in each pure solvent and the data ranked as ethyl acetate > acetone > toluene ≈ benzene > ethanol > methanol > isopropyl alcohol ≈ cyclohexane. The solubility data was well correlated by the modified Apelblat model, NRTL model, van’t Hoff model, and λh model. The solubility curves of diflufenican can be divided into two categories, and the solubilities in ethyl acetate, acetone, toluene, and benzene are quite larger than those in methanol, ethanol, isopropyl alcohol, and cyclohexane. It can be concluded that ethyl acetate, acetone, toluene, and benzene are good solvents for diflufenican while methanol, ethanol, isopropyl alcohol, and cyclohexane can be used as antisolvents. For the binary solvent, the solubility increased significantly with the increasing mole fraction of acetone in both systems, and the solubility surfaces were generated by using the Jouyban−Acree model. The large solubility range indicates that the binary acetone + water solvent mixture is a good selection for the dilution crystallization process of diflufenican.

Table 9. Parameters and Fitting Errors of Jouyban-Acree Model for the Solubility of Diflufenican in Binary Solvent Systems parameters

acetone + water

acetone + ethanol

A1 A2 A3 A4 A5 A6 A7 ARD 108RMSD

3.536 −2920.253 5.380 5135.967 −19108.590 20979.803 −8723.228 1.365 6.773

5.893 −2951.655 0.936 −659.769 −170.594 −249.187 −173.516 1.308 4.739

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +86-451-86403829. Fax: +86-451-86418270.

4.3. Model Correlation. The modified Apelblat model, NRTL model, van’t Hoff model, and λh model are used to correlate the solubility of diflufenican in the pure solvents, and the Jouyban−Acree model is employed to fit the solubility data in the binary solvent systems. The parameters for each model are listed in Tables 5−9 together with the evaluation parameters. The data shows that the maximum ARD values for the correlation models are 1.875% (Apelblat model), 3.482% (NRTL model), 2.604% (van’t Hoff), 2.791% (λh model) and 1.365% (Jouyban−Acree), respectively. The ARD values indicate

ORCID

Liangcheng Song: 0000-0001-8069-4708 Notes

The authors declare no competing financial interest.

■

FUNDING This work is supported by the Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2013044).

Figure 7. Nonlinear surface fit plots of x1 versus T and xs1 for the solubility of diflufenican in binary solvent systems: (a) acetone + water; (b) acetone + ethanol. H

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

■

Article

(19) Guo, C. L.; Li, L. J.; Cheng, J. Y.; Zhang, J. L.; Li, W. Solubility of caprolactam in different organic solvents. Fluid Phase Equilib. 2012, 319, 9−15. (20) Li, J. Q.; Wang, Z.; Bao, Y.; Wang, J. K. Solid-liquid phase equilibrium and mixing properties of cloxacillin benzathine in pure and mixed solvents. Ind. Eng. Chem. Res. 2013, 52, 3019−3026. (21) Renon, H.; Prausnitz, J. M. Local compositions in thermodynamic excess functions for liquid mixtures. AIChE J. 1968, 14, 135−144. (22) Zhang, X.; Yin, Q. X.; Li, X.; Zhang, M. J.; Huang, J. T.; Wang, C.; Zhang, Z. X.; Huang, Y. H.; Guo, M. X.; Li, Y. Solubility and mixing thermodynamics properties of erythromycin ethylsuccinate in different organic solvents. J. Mol. Liq. 2017, 237, 46−53. (23) Choi, W. S.; Kim, K. J. Solubility of Forms I and II of clopidogrel hydrogen sulfate in methanol and 2-propanol mixture. J. Chem. Eng. Data 2011, 56, 43−47. (24) Buchowski, H.; Ksiazczak, A.; Pietrzyk, S. Solvent activity along a saturation line and solubility of hydrogen-bonding solids. J. Phys. Chem. 1980, 84, 975−979. (25) Acree, W. E. Mathematical representation of thermodynamic properties: Part 2. Derivation of the combined nearly ideal binary solvent (NIBS)/Redlich-Kister mathematical representation from a two-body and three-body interactional mixing model. Thermochim. Acta 1992, 198 (1), 71−79. (26) Song, L. C.; Wei, L. H.; Si, T.; Guo, H.; Yang, C. H. Solution thermodynamics of creatine monohydrate in binary (water plus ethanol) solvent systems at T = (278.15 to 328.15) K. J. Chem. Thermodyn. 2016, 92, 139−145. (27) Zong, S. Y.; Wang, J. K.; Xiao, Y.; Wu, H.; Zhou, Y. N.; Guo, Y. M.; Huang, X.; Hao, H. X. Solubility and dissolution thermodynamic properties of lansoprazole in pure solvents. J. Mol. Liq. 2017, 241, 399−406. (28) Gracin, S.; Rasmuson, A. C. Solubility of phenylacetic acid, phydroxyphenylacetic acid, p-aminophenylacetic acid, p-hydroxybenzoic acid, and ibuprofen in pure solvents. J. Chem. Eng. Data 2002, 47, 1379−1383. (29) Li, Q. S.; Lu, F. H.; Tian, Y. M.; Feng, S. J.; Shen, Y.; Wang, B. H. Solubility of veratric acid in eight monosolvents and ethanol+1butanol at various temperatures. J. Chem. Eng. Data 2013, 58, 1020− 1028. (30) Zhou, L. N.; Yin, Q. X.; Guo, Z. Q.; Lu, H. J.; Liu, M. Y.; Chen, W.; Hou, B. H. Measurement and correlation of solubility of ciclesonide in seven pure organic solvents. J. Chem. Thermodyn. 2017, 105, 133−141. (31) Li, S.; Wang, L. Y.; Zhu, M. H.; Han, D. D.; Liu, Y.; Chen, M. Y.; Hou, J. E.; Gong, J. B. Determination and correlation of solubility and thermodynamic properties of&IT trans&IT-cinnamyl alcohol in pure and binary solvents from 253.15 to 293.15 K. J. Chem. Eng. Data 2018, 63, 77−88. (32) Knox, M.; Trifkovic, M.; Rohani, S. Combining anti-solvent and cooling crystallization: Effect of solvent composition on yield and meta stable zone width. Chem. Eng. Sci. 2009, 64, 3555−3563.

ACKNOWLEDGMENTS We also would like to acknowledge Professor Baohua Wang from Beijing University of Chinese Medicine for help with the NRTL model.

■

REFERENCES

(1) Cramp, M. C.; Gilmour, J.; Parnell, E. W. New herbicidal nicotinamide derivatives. Eur. Patent EP0053011B1, 1985. (2) Rouchaud, J.; Gustin, F.; Moulart, C.; Herin, M. Selective cleavage of the ether and amide bonds in N-(2,4-difluorophenyl)-2[3-(trifluoromethyl)-phenoxy]-3-pyridinecarboxamide (diflufenican). Bull. Soc. Chim. Belg. 1990, 99, 339−344. (3) Pepe, G.; Pfefer, G.; Boistelle, R.; Marchal, P. Diflufenican, N(2,4-difluorophenyl)-2-[3-(trifluoromethyl)phenoxy]-3-pyridinecarboxamide. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1995, 51, 2671−2672. (4) Rouchaud, J.; Gustin, F.; Van Himme, M.; Bulcke, R.; Benoit, F.; Maddens, K. Metabolism of the herbicide diflufenican in the soil of field wheat crops. J. Agric. Food Chem. 1991, 39, 968−976. (5) Roberts, H. A.; Bond, W. Evaluation of diflufenican for weed control in drilled vegetable crops. Ann. Appl. Biol. 1986, 108, 96−97. (6) Cramp, M. C.; Gilmour, J.; Hatton, L. R.; Hewett, R. H.; Nolan, C. J.; Parnell, E. W. Design and synthesis of N-(2,4-difluorophenyl)-2(3-trifluoromethylphenoxy)-3-pyridinecarboxamide (diflufenican), a novel pre- and early post-emergence herbicide for use in winter cereals. Pestic. Sci. 1987, 18, 15−28. (7) Knight, H.; Kirkwood, R. C. Cuticular penetration of foliarapplied diflufenican in galium aparine L. Pestic. Sci. 1991, 33, 305− 317. (8) Haynes, C.; Kirkwood, R. C. Studies on the mode of action of diflufenican in selected crop and weed species: Basis of selectivity of pre- and early post-emergence applications. Pestic. Sci. 1992, 35, 161− 165. (9) Ashton, I. A.; Abulnaja, K. O.; Pallett, K. E.; Cole, D. J.; Harwood, J. L. The mechanism of inhibition of fatty acid synthase by the herbicide diflufenican. Phytochemistry 1994, 35, 587−590. (10) Ashton, I. P.; Abulnaja, K. O.; Pallett, K. E.; Cole, D. J.; Harwood, J. L. Diflufenican, a carotenogenesis inhibitor, also reduces acyl lipid synthesis. Pestic. Biochem. Physiol. 1992, 43, 14−21. (11) Gu, Q.; Zhang, X. J. Pyridinecarboxamide herbicide diflufenican. Modern Agrochemicals 2010, 42−45. (12) Hu, W. W.; Wang, S.; Liang, A. Z.; Wang, J. D. Measurement and Correlation of Solubility on Reactive Crystallization of Methyl D(−)-4-Hydroxy-phenylglycinate. J. Chem. Eng. Data 2017, 62, 69−79. (13) Luo, W. P.; Xie, K. L.; Liu, D. W.; Li, X. Q.; Tao, B.; Hao, J.; Deng, W.; Liu, Q.; Guo, C. C. Measurement and Correlation for Solubilities of Adipic Acid, Glutaric Acid, and Succinic Acid in Dimethyl Adipate plus Methanol Mixtures. J. Chem. Eng. Data 2017, 62, 3124−3137. (14) Li, X. B.; Liu, Y.; Cao, Y.; Cong, Y.; Farajtabar, A.; Zhao, H. K. Solubility Modeling, Solvent Effect, and Preferential Solvation of Thiamphenicol in Cosolvent Mixtures of Methanol, Ethanol, N,NDimethylformamide, and 1,4-Dioxane with Water. J. Chem. Eng. Data 2018, 63, 2219−2227. (15) Guo, H.; Song, L. C.; Yang, C. H.; Tao, Y.; Long, Y. J.; Cui, Y. B. Solubility of clopidogrel hydrogen sulfate (Form II) in ethanol plus cyclohexane mixtures at (283.35 to 333.75) K. J. Chem. Eng. Data 2015, 60, 545−550. (16) Korin, E.; Soifer, L. Phase diagram for the system K2Cr2O7+KNO3+H2O in the temperature range 10 degrees C to 40 degrees C. J. Chem. Eng. Data 1997, 42, 508−510. (17) Qin, J. H.; Zeng, Z. X.; Xue, W. L. Experimental measurement and correlation of solubility of pentachloropyridine and tetrachloropyridine in methanol, ethanol, and 2-propanol. J. Chem. Eng. Data 2006, 51, 145−147. (18) Domanska, U.; Kozlowska, M. K. Solubility of imidazoles in ethers. J. Chem. Eng. Data 2003, 48, 557−563. I

DOI: 10.1021/acs.jced.8b00632 J. Chem. Eng. Data XXXX, XXX, XXX−XXX