Solubility Determination and Thermodynamic Modeling of Buprofezin

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

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Solubility Determination and Thermodynamic Modeling of Buprofezin in Different Solvents and Mixing Properties of Solutions Xiaoying Chen,† Zehua Zhou,† Jingjing Chen,† Chu Chu,† Jianli Zheng,† Shiting Wang,† Wenping Jia,† Jia Zhao,‡ Rongrong Li,*,† and Deman Han*,† †

School of Pharmaceutical and Materials Engineering, TaiZhou University, Taizhou, Zhejiang 318000, People’s Republic of China Industrial Catalysis Institute of Zhejiang University of Technology, Hangzhou 310014, People’s Republic of China

J. Chem. Eng. Data Downloaded from pubs.acs.org by WEBSTER UNIV on 02/28/19. For personal use only.

‡

ABSTRACT: In this work, the equilibrium solubility of buprofezin in different pure solvents was determined. The mole solubility of buprofezin in these studied pure solvents increased with increasing temperature. The solubility data decreased according to the following order: toluene > ethyl acetate > DMF > acetone > 1-octanol > 1-butanol > n-propanol > acetonitrile > isopropanol > ethanol > methanol > water. The results were correlated with four thermodynamic models (the modified Apelblat equation, λh equation, NRTL model, and Wilson model), and the values of root-mean-square deviation (RMSD) and relative average deviation (RAD) are no more than 27.26 × 10−4 and 2.76%, respectively. Due to the maximum values of RAD and RMSD were 1.58% and 3.77 × 10−4 in modified Apelblat equation, which indicate that it is a suitable model to describe the results. Besides, the mixing Gibbs energy, mixing enthalpy, and mixing entropy were computed. The values of ΔmixG are negative in this experiment; therefore, the dissolution process is a spontaneous and favorable process, and the ΔmixS are all positive, which indicate the dissolving process is entropy favorable as well. crystallized with methanol.8−11 Therefore, it is of great significance to study the dissolution and purification process of buprofezin in different solvents. It is well-known that the selection of solvents is very important in the process of drug synthesis and separation. Different solvents will have a direct effect on the yield and purity of the product. In the present work, we studied the solution behavior of buprofezin in different solvents at temperatures ranging from 273.15 to 318.15 K by using the isothermal saturation method, correlated the resluts with different thermodynamic models, and furthermore calculated the mixing properties for the solution process of buprofezin in different solvents.

1. INTRODUCTION Buprofezin (CAS No. 69327-76-0) is a chitin synthesis inhibitor introduced by Nihon Nohyaku Co., Ltd. (Tokyo, Japan) and already widely used all the world over.1 It is a thiadiazine insect regulator and molting inhibitor with very low risks to the environment and humans that has a persistent larvicidal action against some Coleoptera and Hemiptera and effectively controls harmful insect pests including the brown rice planthopper (Nilaparvata lugens (N. lugens)) and the greenhouse whitefly (Trialeurodes vaporariorum (T. vaporariorum)).2−4 Buprofezin does not kill adults but can reduce spawning and hinder egg hatching. Although buprofezin lacks an acute insecticidal effect,5,6 it offers the advantage of longer residual activity against N. lugens nymphs than conventional insecticides. Therefore, buprofezin was thought by many researchers to be a unique insecticide for controlling the planthopper in China. Moreover, in recent years, buprofezin has been recommended as one of the main alternatives for replacing methamidophos.7 It is difficult to meet the needs of the pesticide industry. At present, the solvent for the synthesis of buprofezin is mostly toluene or 1,2-dichloroethane and then © XXXX American Chemical Society

2. SOLUBILITY MODELS In this work, based on the experiment results, four models (the modified Apelblat equation, 12,13 λh equation, 14 Wilson Received: November 20, 2018 Accepted: February 20, 2019

A

DOI: 10.1021/acs.jced.8b01099 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

Journal of Chemical & Engineering Data

Article

Table 1. Materials Used in the Work chemicals

molar mass/ (g·mol−1)

melting point/K 377.95a

melting enthalpy/ (kJ·mol−1)

density/ (kg·m−3) (295 K)

30.03a

1120b

Hubei Kang Baotai Fine Chemical 0.995 Co., Ltd., China.

HPLCd

Sinopharm Chemical Reagent Co., 0.997 Ltd., China 0.995 0.995 0.996 0.996 0.995 0.994 0.996 0.996 0.995 0.995 secondary distilled water

none

buprofezin

305.44

methanol

32.04

786.5c

46.07 60.06 60.06 74.12 130.23 58.05 92.14 88.11 41.05 73.09 18.01

789.3c 805.3c 803.5c 809.8c 827c 784.5c 871.0c 900.3c 776.8c 948d 1c

source

mass fraction purity

analysis method

377.65−378.15c,e

ethanol n-propanol isopropanol 1-butanol 1-octanol acetone toluene ethyl acetate acetonitrile DMF water

a This work, determined at 101.2 kPa. The standard uncertainties u are u(T) = 0.5 K, u(p) = 0.45 kPa, and u(ΔfusH) = 0.4 kJ·mol−1. bCalculated with the Advanced Chemistry Development (ACD/Laboratories) Software V11.02 (1994−2016 ACD/Laboratories). cTaken from ref 1. dHighperformance liquid phase chromatograph. eTaken from ref 20.

model,15 and NRTL model16) are employed to correlate the experimental solubility. 2.1. Modified Apelblat Equation. This semiempirical equation is usually used to describe the dependence of solubility data on the temperature and shown in eq 1.12,13 B ln x = A + + C ln T T

describing the solubility of solute in different solvents can be deduced from eq 4.15 ln(xiγi) =

(4)

while the activity coefficient of solute can be obtained by Wilson eq 17 ÄÅ ÉÑ ÅÅ ÑÑ Λ 21 Λ12 Å ÑÑ Å ln γ1 = −ln(x1 + Λ12x 2) + x 2ÅÅ − Ñ ÅÅÇ x1 + Λ12x 2 x 2 + Λ 21x1 ÑÑÑÖ

(1)

where A, , and C are the adjustable parameters, x is the mole fraction solubility data, and T represents the experimental temperature in kelvin. 2.2. Buchowski−Ksiazaczak λh Equation. The λh equation is another semiempirical, which is first put forward by Buchowski and co-workers and has two adjustable parameters (λ and h).14 ÄÅ É ij 1 ÅÅ λ(1 − x) ÑÑÑÑ 1 yzz lnÅÅÅ1 + ÑÑ = λhjjj − z jT ÅÅÇ ÑÑÖ x Tm zz{ (2) k

Λ12 =

Λ 21 =

V2 i λ − λ11 zy V2 i Δλ y zz = expjjj− 12 expjjj− 12 zzz V1 RT V k { k RT { 1

V1 V i λ − λ11 yz i Δλ y zz = 1 expjjj− 21 zzz expjjj− 21 V2 RT { V2 k k RT {

(5)

(6)

(7)

Here V1 and V2 are the molar volumes of solute and solvent. Δλij are the interaction parameters (J·mol−1). 2.4. NRTL Model. Based on the local composition concept, the NRTL model is applied to correlate the results of solubility as well.16,17 the model can be expressed by eqs 8−11. ÄÅ ÉÑ N N N ∑ j = 1 τjiGjixj ∑i = 1 xiτijGij ÑÑÑÑ xjGij ÅÅÅÅ ÅÅτij − ÑÑ ln γi = +∑ N N N ÅÅ ÑÑ ∑i = 1 Gijxi ∑ ∑ G x G x Å ÑÑÖ ij i ij i j=1 i=1 i=1 ÅÇ

In eq 2, Tm is the melting temperature of buprofezin in kelvin. 2.3. Wilson Equation. According to the theory of solid− liquid phase equilibrium, at a fixed temperature and pressure, once a solid−liquid system arrives at equilibrium, the solubility data of solute at different temperatures can be expressed as eq 3.15 ln(xiγi) =

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

yz ΔHtp ijj 1 1 yzzz ΔCp ijj ijj Ttp yzz Ttp jj jjlnjj zz − − + 1zzzz zz − j j R j Ttp Tz R k kT { T { k { ΔV − (p − ptp ) (3) RT

(8)

Gji = exp( −αjiτji)

(9)

αij = αji = α

where γ stands for the activity coefficient of a solute; also x is mole fraction solubility of a solute in solvent; and R is the universal gas constant, having a value of 8.314 J·K−1·mol−1. ΔV and ΔCp stand for the difference of volume and heat capacity of a solute between in solid phase and in liquid phase at the melting temperature, respectively. The simple equation

τij =

gij − gjj RT

(10)

=

Δgij RT

(11)

Δgij are model parameters (J·mol−1). α exhibits the nonrandomness of the solution (varies from 0.20 to 0.47). B



Article

liquid phase became constant. The analysis results showed that 12 h can ensure the solution equilibrium. Then the magnetic stirrer was stopped, and the solid was allowed to precipitate from the mixture. A 2 mL aliquot of solution was taken out and transferred instantaneously to a 25 mL preweighted volumetric flask, weighed again, and diluted with corresponding solvents; after that, 5 μL of the solution was tested with HPLC. During the experiment, the analysis conditions are as follows: a reverse phase column having a type of LP-C18 (250 mm × 4.6 mm), and the temperature was 303.15 K. The wavelength of the UV detector was 250 nm. Pure methanol at a flow rate of 1.0 mL·min−1 was the mobile phase.

In the Wilson model (Δλij) and NRTL model (Δgij), assuming the binary cross-interaction parameters are a linear relationship with temperature,18 the Λij in Wilson model and τij in NRTL model can be expressed as eqs 12 and 13, respectively. ÄÅ É ÅÅ i bij yzÑÑÑÑ Vj ÅÅ jj z expÅÅ−jjaij + zzÑÑÑ Λij = ÅÅ j T z{ÑÑÑÖ Vi (12) ÅÇ k τij = aij +

bij T

(13)

where aij and bij are model parameters.

4. RESULTS AND DISCUSSION 4.1. Property of Thermodynamics. The DSC curve of buprofezin is shown in Figure 1; the melting temperature Tm

3. EXPERIMENTAL SECTION 3.1. Materials. Buprofezin was provided by Hubei Kang Baotai Fine Chemical Co., Ltd., China (with a mass fraction of 0.976). It was purified three times via crystallization in methanol and had a mass fraction purity of 0.995 (determined by the high-performance liquid phase chromatograph). During the experiment, the solvents with analytical grade were purchased from Sinopharm Chemical Reagent Co., Ltd., China and used without any additional purification. The detailed information on these materials was presented in Table 1. 3.2. Properties Measurement. Up to now, the melting temperature Tm = 278.15 K of buprofezin has been determined by Syracuse Research Corp. of Syracuse, New York (USA); however, ΔfusH (the enthalpy of fusion) has not been reported. In this work, a differential scanning calorimetric instrument (Pyris-Diamond, PerkinElmer) was applied to determine the ΔfusH of buprofezin (precalibrated before experiment, under a nitrogen atmosphere). Indium is the reference material. Samples weighed about 5 mg are placed in a DSC pan and heated at a rate of 2 K·min−1 (within the temperature range from 293.15 to 410.15 K). The standard uncertainties of the temperature were estimated to be 0.5 K and 400 J·mol−1 for the melting enthalpy. 3.3. X-ray Diffraction Investigations. In order to validate the existence of the polymorph transformation or solvate formation of buprofezin during the mutual solubility determination, X-ray powder diffraction (XPRD) was used to analyze the crystal form of buprofezin before and after measurement. The operation process performed by the Rigaku D/max-2500 with Cu Kα radiation (λ = 1.54184 Å). After that, adjusting the voltage and current of the tube and then collecting the values from 10° to 50° (2θ) at a scan speed of 6 deg·min−1 under atmospheric pressure. 3.4. Solubility Determination. Before the experimental, the reliability of verification of experiment apparatus was verified in our previous work.19 The apparatus for the solubility determination including a 100 mL jacketed glass vessel with a condenser, a magnetic stirrer. and circulating water system. The temperature of the circulating water was controlled by a smart thermostatic water bath (Model: DZKW-4) with the standard uncertainty of 0.02 K. Excess buprofezin was added into the jacketed glass vessel (with 60 mL of solvent). In order to mix the solution sufficiently, the magnetic stirrer was applied. The true temperature was shown by a mercury glass microthermometer. Using a 2 mL syringe connected with a 0.2 μm pore filter to take out the liquid phase every 2 h and tested by HPLC. The solution was assumed to be in equilibrium once the composition of the

Figure 1. DSC curve of buprofezin.

and melting enthalpy ΔfusH of buprofezin are 377.95 K and 30.03 kJ·mol−1, respectively. The value of melting temperature Tm determined in this work (377.95 K) is very close to the values that were reported by Dessouki and co-workers.1 It may be caused by the difference in equipment, purity, and purification method. 4.2. Results of PXRD Patterns for Buprofezin. The tested results of the PXRD patterns for buprofezin in pure solvents before and after experiment are presented in Figure 2.

Figure 2. PXRD patterns of buprofezin in different solvents and raw material. C



Article

Table 2. Experimental and Calculated Mole Fraction Solubility (x) of Buprofezin in 12 Pure Solvents at T= 273.15−318.15 K under 101.2 kPaa x xexp

T/K 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

3.771 4.972 6.401 7.968 9.980 1.230 1.540 1.838 2.247 2.723

× × × × × × × × × ×

10−3 10−33 10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2

100RAD

xλh

xApelblat 3.874 4.972 6.322 7.967 9.958 1.235 1.519 1.856 2.253 2.716

× × × × × × × × × ×

10−3 10−3 10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2

Methanol 3.930 4.986 6.284 7.872 9.808 1.216 1.503 1.851 2.274 2.791

0.74

× × × × × × × × × ×

xWilson 10−3 10−3 10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2

1.72

3.898 4.966 6.281 7.888 9.846 1.222 1.509 1.855 2.273 2.776

× × × × × × × × × ×

10−3 10−3 10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2

1.44

xNRTL 3.872 × 10−3 4.955 × 10−3 6.289 × 10−3 7.92 × 10−3 9.899 × 10−3 1.229 × 10−2 1.515 × 10−2 1.858 × 10−2 2.264 × 10−2 2.746 × 10−2 0.94

Ethanol 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

5.385 6.996 9.173 1.157 1.464 1.817 2.282 2.757 3.418 4.248

× × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

100RAD 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

1.23 5.642 7.981 1.101 1.481 1.903 2.536 3.235 4.141 5.282 6.677

× × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

100RAD 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

5.917 × 10−3 8.077 × 10−3 1.09 × 10−2 1.453 × 10−2 1.918 × 10−2 2.506 × 10−2 3.244 × 10−22 4.159 × 10−2 5.288 × 10−2 6.668 × 10−2 1.19

5.864 7.852 1.028 1.305 1.650 2.070 2.540 3.098 3.757 4.537

× × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

100RAD 273.15 278.15 283.15 288.15 293.15

5.568 × 10−3 7.135 × 10−3 9.084 × 10−3 1.15 × 10−2 1.447 × 10−2 1.811 × 10−2 2.255 × 10−2 2.793 × 10−2 3.443 × 10−2 4.226 × 10−2

6.008 × 10−3 7.879 × 10−3 1.02 × 10−2 1.303 × 10−2 1.646 × 10−2 2.056 × 10−2 2.541 × 10−2 3.109 × 10−2 3.768 × 10−2 4.527 × 10−2 0.56

6.270 9.080 1.275 1.667 2.176

× × × × ×

10−3 10−3 10−2 10−2 10−2

6.720 9.197 1.240 1.650 2.168

× × × × ×

10−3 10−3 10−2 10−2 10−2

5.505 7.078 9.032 1.145 1.442 1.806 2.251 2.794 3.458 4.268 1.25 n-Propanol 5.895 8.018 1.079 1.438 1.899 2.486 3.228 4.161 5.326 6.777 1.51 Isopropanol 6.182 7.932 1.010 1.278 1.606 2.008 2.498 3.096 3.823 4.710 2.32 1-Butanol 6.764 9.137 1.222 1.618 2.123

D

× × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

5.471 7.057 9.029 1.147 1.446 1.812 2.258 2.800 3.456 4.249

× × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

1.02 × × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

5.876 7.994 1.077 1.436 1.898 2.487 3.233 4.171 5.341 6.794

10−3 10−33 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

6.130 7.896 1.009 1.279 1.611 2.016 2.509 3.105 3.826 4.696

× × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

10−3 10−3 10−2 10−2 10−2

6.726 9.096 1.218 1.615 2.122

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

5.669 7.962 1.093 1.470 1.940 2.523 3.242 4.133 5.255 6.699

× × × × × × × × × ×

10−3 10−3 10−2 10− 10− 10−2 10−2 10−2 10−2 10−2

× × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

× × × × ×

10−3 10−3 10−2 10−2 10−2

0.59 × × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

2.07 × × × × ×

× × × × × × × × × ×

0.77

1.54 × × × × × × × × × ×

5.414 7.035 9.051 1.153 1.457 1.826 2.270 2.803 3.439 4.196

6.086 7.878 1.010 1.285 1.621 2.028 2.520 3.109 3.810 4.639 1.60

× × × × ×

10−3 10−3 10−2 10−2 10−2

6.345 9.018 1.246 1.677 2.204



Article

Table 2. continued x T/K 298.15 303.15 308.15 313.15 318.15

x 2.810 3.639 4.496 5.773 7.138

exp

× × × × ×

10−2 10−2 10−2 10−2 10−2

100RAD 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

x

2.812 3.606 4.574 5.741 7.136

× × × × ×

10−2 10−2 10−2 10−2 10−2

1-Butanol 2.763 3.567 4.572 5.820 7.365

10−3 10−2 10−2 10−2 10−2 10−2 10−22 10−2 10−2 10−2

2.74 1-Octanol 8.602 1.137 1.488 1.931 2.486 3.177 4.031 5.082 6.370 7.943

1.58 8.244 1.140 1.515 1.974 2.514 3.208 4.038 5.048 6.299 7.886

× × × × × × × × × ×

10−3 10−2 10−2 10−2 10−22 10−2 10−2 10−2 10−2 10−2

100RAD

xλh

Apelblat

8.712 1.149 1.501 1.945 2.500 3.188 4.036 5.073 6.334 7.858

× × × × × × × × × ×

1.14

× × × × ×

× × × × × × × × × ×

xWilson 10−2 10−2 10−2 10−2 10−2

10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

1.34

2.766 3.576 4.587 5.843 7.391

× × × × ×

xNRTL

10−2 10−2 10−2 10−2 10−2

2.839 3.602 4.529 5.686 7.191

2.76

2.61

8.562 × 10−3 1.133 × 10−2 1.486 × 10−2 1.931 × 10−2 2.489 × 10−2 3.183 × 10−2 4.04 × 10−2 5.093 × 10−2 6.378 × 10−2 7.937 × 10−2

8.460 1.129 1.489 1.944 2.512 3.213 4.070 5.106 6.343 7.805

1.31

1.08

× × × × ×

10−2 10−2 10−2 10−2 10−2

× × × × × × × × × ×

10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−2 10− 10−1 10−1

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1 10−1 10−1

Acetone 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

3.000 3.613 4.271 5.041 5.929 6.995 8.141 9.604 1.140 1.337

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1

100RAD

3.054 3.602 4.249 5.010 5.907 6.961 8.200 9.656 1.136 1.336

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−22 10−2 10−22 10−1 10−1

2.988 3.577 4.261 5.055 5.973 7.033 8.257 9.670 1.130 1.319

0.57

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1

0.75

3.018 3.594 4.261 5.034 5.932 6.977 8.199 9.636 1.134 1.337

× × × × × × × × × ×

10−2 10−2 10−2 10−22 10−2 10−2 10−2 10−2 10−1 10−1

0.34

3.018 3.593 4.261 5.034 5.932 6.977 8.199 9.636 1.134 1.337 0.35

DMF 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

3.064 3.890 4.926 6.080 7.251 8.714 1.039 1.220 1.407 1.618

× × × × × × × × × ×

10−2 10−22 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

100RAD

3.085 3.912 4.885 6.014 7.304 8.759 1.038 1.216 1.410 1.618

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

3.218 3.960 4.841 5.879 7.098 8.522 1.018 1.210 1.432 1.688

0.51

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

2.51

3.187 3.943 4.841 5.898 7.134 8.570 1.023 1.213 1.430 1.676

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

2.07

3.066 3.907 4.893 6.030 7.321 8.767 1.037 1.214 1.407 1.620 0.44

Toluene 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

5.304 6.511 7.816 9.236 1.098 1.283 1.498 1.724 1.981 2.271

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1 10−1 10−1

5.352 6.484 7.784 9.268 1.095 1.284 1.494 1.728 1.985 2.267

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1 10−1 10−1

5.426 6.509 7.759 9.197 1.084 1.272 1.484 1.725 1.996 2.300

E

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1 10−1 10−1

5.370 6.484 7.769 9.240 1.091 1.280 1.492 1.728 1.990 2.279

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1 10−1 10−1

5.373 6.489 7.772 9.237 1.090 1.278 1.489 1.726 1.993 2.291



Article

Table 2. continued x T/K

x

exp

xλh

Apelblat

x

xWilson

xNRTL

Toluene 100RAD 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

0.33 3.725 4.654 5.610 6.791 8.150 9.707 1.157 1.358 1.595 1.872

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

100RAD 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

3.772 4.617 5.614 6.781 8.140 9.715 1.153 1.361 1.599 1.869

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

0.86 Ethyl Acetate 3.774 4.616 5.608 6.770 8.126 9.699 1.152 1.361 1.601 1.875

10−3 10−3 10−2 10−22 10−2 10−2 10−2 10−2 10−2 10−22

0.41 Acetonitrile 5.655 7.547 9.975 1.307 1.698 2.191 2.806 3.572 4.523 5.699

0.35 5.340 7.743 1.015 1.332 1.709 2.194 2.845 3.542 4.481 5.639

× × × × × × × × × ×

10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2 10−2

100RAD

5.712 7.616 1.006 1.317 1.710 2.202 2.813 3.569 4.496 5.626

× × × × × × × × × ×

1.34

0.46 × × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

3.754 4.607 5.612 6.787 8.152 9.730 1.154 1.362 1.598 1.867

0.56 × × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

0.31 × × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

1.70

5.633 7.526 9.960 1.306 1.700 2.194 2.812 3.580 4.530 5.699

3.741 4.612 5.627 6.804 8.161 9.724 1.152 1.358 1.597 1.872

× × × × × × × × × ×

10−2 10−2 10−2 10−2 10−2 10−2 10−1 10−1 10−1 10−1

× × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

× × × × × × × × × ×

10−5 10−5 10−5 10−5 10−5 10−5 10−5 10−4 10−4 10−4

0.27 × × × × × × × × × ×

10−3 10−3 10−3 10−2 10−2 10−2 10−2 10−2 10−2 10−2

1.70

5.581 7.502 9.976 1.313 1.712 2.210 2.828 3.587 4.510 5.622 1.45

Water 273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 100RAD

2.841 3.479 4.182 5.080 6.049 7.257 8.541 1.008 1.204 1.439

× × × × × × × × × ×

10−5 10−5 10−5 10−5 10−5 10−5 10−5 10−4 10−4 10−4

2.899 3.489 4.191 5.024 6.012 7.179 8.557 1.018 1.209 1.433

× × × × × × × × × ×

10−5 10−5 10−5 10−5 10−5 10−5 10−5 10−4 10−4 10−4

2.884 3.482 4.187 5.018 5.999 7.158 8.531 1.016 1.212 1.447

0.73

0.73

× × × × × × × × × ×

10−5 10−5 10−5 10−5 10−5 10−5 10−5 10−4 10−4 10−4

2.855 3.469 4.193 5.044 6.041 7.209 8.577 1.018 1.207 1.430 0.49

× × × × × × × × × ×

10−5 10−5 10−5 10−5 10−5 10−5 10−5 10−4 10−4 10−4

2.837 3.475 4.214 5.067 6.054 7.202 8.545 1.014 1.204 1.437 0.29

a

x denotes the experimental mole fraction solubility; RAD is the relative deviation and the relative average deviation, respectively. Standard uncertainties u are u(T) = 0.02 K and u(p) = 450 Pa; relative standard uncertainty ur is ur(x) = 0.041. xexp, experiment data; xApelblat, calculated by Apelblat model; xλh, calculated by λh model; xWilson, calculated by Wilson model; xNRTL, calculated by NRTL model.

In order to elucidate the difference of solubility of buprofezin in different solvents, the properties of the selected solvents, including polarities, dipole moments (μ), dielectric constants (ε), and Hildebrand solubility parameters (δH) are collected and tabulated in Table 3.20 Tables 2 and 3 further demonstrate that the solubility of buprofezin in six alcohols decreases with the increase in polarities, dielectric constants, and Hildebrand solubility parameters. Moreover, in other solvents, solubility values decrease with the increase in polarities and dielectric constants except for acetone. In addition to acetonitrile and water, the solubility in alcohol solvents is obviously smaller than that in other solvents. The polarity may be an important factor that influences the solubility of buprofezin in the selected solvents. The polarity

It can be seen that all the XPRD patterns of solid phase of buprofezin in equilibrium with its solution have the same characteristic peaks with the raw material. Therefore, no polymorph transformation or solvate formation is observed during the whole experiment. 4.3. Solubility Data. The determined solubility in mole fraction of buprofezin in 12 pure solvents within the temperature range from 273.15 to 318.15 K are presented in Table 2 and shown graphically in Figure 3. From this figure, the result of solubility data increases with increasing temperature. According to the following order: toluene > ethyl acetate > DMF > acetone > 1-octanol > 1-butanol > npropanol > acetonitrile > isopropanol > ethanol > methanol > water. They decrease in different solvents. F



Article

Figure 3. Solubility (x) of buprofezin in mole fraction in 12 pure solvents over a temperature range from 273.15 to 318.15 K.

Table 3. Physical Properties for the Selected Solventsa solvent

polarity (water 100)

μ(298 K)/D

ε(293K)/ (F·m−1)

δH(298K)/ (cal1/2·cm−3/2)

methanol ethanol n-propanol isopropanol 1-butanol 1-octanol toluene acetone acetonitrile ethyl acetate DMF water

76.2 65.4 61.7 54.6 60.2 0.9 9.9 35.5 46 23 40.4 100

1.7 1.7 1.7 1.66 1.66 0 0.4 2.9 3.2 1.7 3.8 1.87

32.6 22.4 20.1 18.3 18.2 1.84 2.38 20.6 37.5 6.02 36.7 79.7

14.5 13.4 11.9 11.5 24.1 7.0 8.9 10.0 11.9 9.1 12.1 23.4

4.4. Solubility Correlation and Calculation. The solubility is correlated with the eqs 1−13 by using the nonlinear regression method. However, the objective function is described as eqs 14 and 15 for Wilson and NRTL models.21 F=

∑ (ln γie − ln γic)2

(14)

i=1

For modified Apelblat equation and λh equation, the objective function is defined as F=

∑ (xie − xic)2

(15)

i=1

In eqs 14 and 15, ln γei and ln γci are the logarithms of experimental and computed activity coefficients. Furthermore, the relative deviation (RD), relative average deviation and (RAD), and root-mean-square deviation (RMSD) are employed to estimate the thermodynamic models, which are expressed as eqs 16 and 17, respectively.

a

Taken from ref 20.

of buprofezin molecule is weak. However, the polarity of these alcohols is relatively strong, so the data in alcohol and water are small. From the data summarized above, interpreting the order of solubility based on a single factor is obviously not feasible. It indicates that the solubility is affected not only by polarity but also by different types of interactions in the system such as Hildebrand solubility parameters, dielectric constants, and dipole moments, and the role of hydrogen bonds, van der Waals forces, and so on.

RAD =

1 N

N

∑

xie − xic xie

ÅÄÅ N ÑÉ1/2 ÅÅ ∑i = 1 (xic − xie)2 ÑÑÑ Å ÑÑ RMSD = ÅÅÅ ÑÑ ÅÅ ÑÑ N ÅÇ ÑÖ i=1

(16)

(17)

Here N is the number of experimental data points; are calculated and experimental values, respectively.

xci

and xei

Table 4. Parameters of the Modified Apelblat Equation and λh Equation for Buprofezin in Different Solvents λh equation

modified Apelblat equation solvent

A

B

C

10 RMSD

λ

h

104RMSD

methanol ethanol n-propanol isopropanol 1-butanol 1-octanol acetone toluene ethyl acetate acetonitrile DMF water

19.053 −43.161 30.416 87.499 84.403 −4.550 −113.946 51.750 1.871 −4.886 152.918 −94.599

−4238.283 −1610.918 −5488.571 −7349.461 −7763.996 −3571.206 2472.520 −4746.230 −2819.250 −3717.524 −9570.692 1117.067

−1.620 7.820 −2.754 −11.712 −10.87 2.296 18.076 −6.649 0.922 2.376 −21.632 14.271

1.02 2.05 1.84 0.93 3.44 2.55 3.70 3.50 2.97 2.01 3.77 0.01

0.1365 0.2428 0.6638 0.2644 0.6856 0.6136 0.4037 0.8677 0.8113 0.4658 0.7539 0.0004

25775.650 15432.037 7014.591 14057.403 6640.575 6860.019 6458.516 3156.372 3735.831 9342.564 4134.697 6696244.30

2.80 2.35 4.23 6.62 8.80 3.88 8.05 13.38 3.66 3.19 27.26 0.01

4

G



Article

Table 5. Parameters of the Wilson and NRTL Models for Buprofezin in Different Solvents Wilson model

NRTL model

solvent

a12

b12/K

a21

b21/K

104RMSD

a12

b12/K

a21

b21/K

α

104RMSD

methanol ethanol n-propanol isopropanol 1-butanol 1-octanol acetone toluene ethyl acetate acetonitrile DMF water

−1.060 −1.721 −4.496 −1.443 −4.160 −2.690 2.994 −0.348 −0.396 −3.840 −1.272 5.830

6.822 200.495 1020.497 181.796 932.974 612.315 −1166.337 −646.989 −469.265 740.655 −333.573 −732.333

16.427 14.487 15.796 −148.188 14.206 14.725 0.616 14.241 2.076 14.444 19.829 5.695

2987.291 3210.399 2665.250 67786.946 1877.864 2778.900 137.108 2385.459 30.431 2566.480 2908.380 25.144

2.31 2.14 4.87 6.11 9.70 3.97 3.06 5.71 3.09 3.32 22.64 0.01

7.188 −18.270 −42.128 7.688 5.557 7.862 −1.151 −1.507 −17.975 7.793 −24.212 −28.423

0.925 12467.833 15660.264 31.164 −0.462 119.554 142.028 261.260 7750.816 97.423 10794.217 11097.672

0.401 0.143 −10.102 −0.678 1.149 −2.781 5.530 3.495 −4.388 −2.685 −5.429 3.147

−87.924 330.079 2946.021 101.118 781.051 600.837 −1394.470 −1038.400 688.082 684.671 1195.185 680.054

0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.3 0.2 0.2 0.2 0.2

1.46 2.40 1.75 4.19 0.09 3.87 3.08 8.85 2.39 2.35 4.05 0.003

Figure 4. Calculated mixing Gibbs energy at measured solubility points based on the Wilson model.

Here x1 is the mole fraction of solute; and x2, the corresponding solvent. For nonideal solution, the three mixing properties can be described as eqs 21 and 22.

During the correlation process, the densities of the selected solvents and buprofezin are presented in Table 1. The melting temperature and melting enthalpy (ΔfusH) of buprofezin were taken from this wok. The regressed parameters’ values A, B, and C in the modified Apelblat equation, λ and h in λh equation, and aij and bij in Wilson model and NRTL model, together with the RMSD values are listed in Tables 4 and 5, respectively. Moreover the acquired values of RAD are tabulated in Table 2. The results show that the calculated and experimental values agree very well. The maximum value of RMSD is 27.26 × 10−4, which is obtained with λh equation in ethyl acetate. The RAD values are all less than 2.76%. For the modified Apelblat equation, the values of RAD are no greater than 1.58%, and the maximum value of RMSD is 3.77 × 10−4, indicating that the modified Apelblat equation is a more suitable model to describe solubility data. 4.5. Mixing Properties of Solutions. Based on the Lewis−Randall rule, the actual states of the pure components are standard states. Therefore, the mixing properties of solutions may be calculated. For an ideal binary solution, the mixing Gibbs energy, mixing enthalpy, and mixing entropy are described as22 Δmix Gid = RT (x1 ln x1 + x 2 ln x 2)

(18)

Δmix S id = −R(x1 ln x1 + x 2 ln x 2)

(19)

id

Δmix H = 0

Δmix M = ME + Δmix M id

(21)

For M = G , H , and S

(22)

Here ME refers to the excess property in nonideal solutions. ΔmixG, ΔmixH, and ΔmixS are the mixing Gibbs energy, mixing enthalpy, and mixing entropy, respectively. The superscript id refers to ideal state. The excess mixing properties can be evaluated by using eqs 23−2523 GE = RT (x1 ln γ1 + x 2 ln γ2) = −RT[x1 ln(x1 + x 2 Λ12) + x 2 ln(x 2 + x1Λ 21)]

ÅÄÅ ÑÉ Å ∂(GE /T ) ÑÑÑ ÑÑ HE = −T 2ÅÅÅÅ ÅÅÇ ∂T ÑÑÑÖ

(23)

ij b Λ b21Λ 21 yzz = x1x 2jjj 12 12 + z jx + Λ x x 2 + Λ 21x1 zz{ 12 2 k 1

SE =

(20) H

HE − GE T

(24)

(25) DOI: 10.1021/acs.jced.8b01099 J. Chem. Eng. Data XXXX, XXX, XXX−XXX


Article

Table 6. Calculated Values of the Mixing Gibbs Energy (ΔmixG), Mixing Enthalpy (ΔmixH), and Mixing Entropy (ΔmixS), Respectively T/K

ΔmixG/ (J·mol−1)

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

−40.16 −50.77 −62.77 −75.39 −90.66 −107.39 −128.17 −147.37 −171.69 −198.05

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

−62.61 −80.30 −100.81 −123.16 −149.48 −179.71 −211.88 −247.86 −287.75 −331.82

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

−317.7 −368.44 −420.07 −477.09 −538.93 −608.33 −678.02 −760.31 −852.76 −945.16

273.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

−57.12 −78.58 −99.53 −125.73 −155.59 −191.9 −237.37 −284.14 −342.36 −408.95

ΔmixH/ (J·mol−1) Methanol 0.2119 0.2786 0.3574 0.4432 0.5524 0.677 0.8413 0.9969 1.2067 1.4456 Isopropanol 8.7827 11.7255 15.2966 19.3407 24.3329 30.3446 36.9886 44.7631 53.7887 64.2559 Acetone −241.931 −288.098 −336.117 −390.367 −450.209 −518.285 −586.285 −666.549 −754.922 −838.161 Acetonitrile 32.587 47.088 61.532 80.427 102.725 131.137 168.795 208.586 261.265 324.856

ΔmixS/ (J·K−1·mol−1)


0.1478 0.1835 0.2229 0.2632 0.3112 0.3624 0.4256 0.4815 0.5521 0.627

−57.15 −71.6 −90.02 −109.49 −133.04 −158.81 −190.47 −221.4 −261.15 −306.91

0.2614 0.3309 0.4101 0.4945 0.5929 0.7045 0.8209 0.9496 1.0907 1.2449

−67.31 −92.78 −124.22 −156.85 −197.07 −244.68 −303.07 −361.77 −441.28 −522.3

0.277 0.289 0.296 0.301 0.303 0.302 0.303 0.304 0.312 0.336

−562.53 −664.39 −768.74 −876.14 −999.24 −1121.35 −1252.45 −1379.49 −1510.73 −1643.14

0.328 0.452 0.569 0.715 0.881 1.083 1.34 1.599 1.928 2.306

−326.85 −398.59 −483.15 −572.08 −658.07 −758.34 −865.46 −973.35 −1077.53 −1185.76

ΔmixH/ (J·mol−1) Ethanol 8.8925 11.5222 15.054 18.9149 23.8173 29.3966 36.6523 43.9593 53.9468 66.1987 1-Butanol 48.204 69.583 97.322 126.759 164.68 211.466 271.903 333.66 424.027 518.855 Toluene −282.632 −345.985 −413.983 −487.337 −576.507 −669.827 −776.573 −886.535 −1008.645 −1142.342 DMF −84.2 −106.598 −134.495 −165.298 −196.238 −234.448 −277.573 −323.317 −369.609 −420.623

ΔmixS/ (J·K−1·mol−1)


0.2418 0.2988 0.3711 0.4456 0.5351 0.6312 0.7492 0.8614 1.0062 1.1727

−60.19 −81.55 −107.88 −139.38 −173.38 −220.6 −270.81 −331.82 −403.62 −485.44

0.423 0.584 0.782 0.984 1.234 1.53 1.897 2.257 2.763 3.273

−87.90 −116.29 −148.55 −186.20 −228.6 −279.97 −338.15 −404.73 −481.56 −571.07

1.025 1.145 1.253 1.349 1.442 1.514 1.57 1.6 1.603 1.574

−394.51 −474.02 −552.3 −643.44 −742.19 −848.24 −965.87 −1083.62 −1210.43 −1343.86

0.888 1.05 1.231 1.412 1.575 1.757 1.939 2.109 2.261 2.405

−0.30 −0.36 −0.41 −0.48 −0.55 −0.63 −0.72 −0.81 −0.92 −1.04

ΔmixH/ (J·mol−1) n-Propanol 47.4326 66.898 91.9585 123.1821 157.6157 208.7264 264.5612 335.9442 424.3366 530.2378 1-Octanol 41.585 57.33 75.928 98.533 124.914 158.482 198.153 245.743 303.655 375.478 Ethyl Acetate −140.54 −174.901 −209.924 −252.722 −301.286 −355.982 −420.058 −487.371 −564.251 −650.493 Water −0.17 −0.21 −0.25 −0.30 −0.36 −0.43 −0.50 −0.58 −0.69 −0.81

ΔmixS/ (J·K−1·mol−1) 0.394 0.5337 0.7058 0.9112 1.1291 1.44 1.766 2.167 2.644 3.1924 0.474 0.624 0.793 0.988 1.206 1.471 1.769 2.111 2.507 2.975 0.93 1.075 1.209 1.356 1.504 1.651 1.8 1.935 2.063 2.179 0.0005 0.0005 0.0006 0.0006 0.0007 0.0007 0.0007 0.0007 0.0007 0.0007

entropy favorable. Therefore, the process of dissolving is apparently not only spontaneous but also entropy-driving

Based on the parameters of the Wilson model, the values of ΔmixG, ΔmixH, and ΔmixS are computed and tabulated in Table 6. The mixing Gibbs energy (ΔmixG) illustrates the dissolution capacity of buprofezin in different solvents and is plotted in Figure 4. The results show that the values of ΔmixG are all negative and decrease with increasing temperature, so the solution process of buprofezin is spontaneous and favorable in the selected solvents. In toluene, acetone, ethyl acetate, DMF, and water, the negative values of ΔmixH demonstrate that the solution procedure is exothermic. However, in other solvents, the enthalpy is positive and belongs to an endothermic process. As seen in Table 6, the ΔmixS was positive in this experiment, which indicated the dissolving process was

5. CONCLUSION The equilibrium solubilities of buprofezin in different pure solvents within the temperature range from 273.15 to 318.15 K were determined. The results increase with increasing temperature, and they decrease according to the following order in different solvents: toluene > ethyl acetate > DMF > acetone > 1-octanol > 1-butanol > n-propanol > acetonitrile > isopropanol > ethanol > methanol > water. Moreover, the results were correlated with four different thermodynamic models, and the maximum values of RMSD and RAD are I



Article

27.26 × 10−4 and 2.76%, respectively. For the modified Apelblat equation, the values of RAD are no greater than 1.58%, and the maximum value of RMSD is 3.77 × 10−4; it is more suitable to describe the solubility behavior of buprofezin. Besides, the mixing Gibbs energy, mixing enthalpy, and mixing entropy were computed. The values of ΔmixG are all negative and decrease with increasing temperature; therefore, the solution process of buprofezin in the studied solvents is spontaneous and favorable, and the ΔmixS was positive in this experiment, which indicated the dissolving process was entropy favorable.

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synthesis of 2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4one. CN Pat. 101,863,859, Oct. 20, 2010. (11) Jiang, Y. T.; An, L. R.; Ji, Y. X.; Wang, H. C.; Wang, J. S. Method for preparing buprofezin and its intermediates. CN Pat. 101,177,418, May 14, 2008. (12) Apelblat, A.; Manzurola, E. 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. (13) 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. (14) 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. (15) Wilson, G. M. Vapor-liquid equilibrium. XI. A new expression for the excess free energy of mixing. J. Am. Chem. Soc. 1964, 86, 127− 130. (16) Renon, H.; Prausnitz, J. M. Estimation of parameters for the NRTL equation for excess Gibbs energies of strongly nonideal liquid mixtures. Ind. Eng. Chem. Process Des. Dev. 1969, 8, 413−419. (17) Yao, G. B.; Xia, Z. X.; Li, Z. H. Thermodynamic study of solubility for 2-amino-4-chloro-6-methoxypyrimidine in twelve organic solvents at temperatures from 273.15 to 323.15 K. J. Chem. Thermodyn. 2017, 105, 187−197. (18) Li, R. R.; Wang, J.; Xu, R. J.; Du, C. B.; Han, S.; Meng, L.; Zhao, H. K. Solubility and dissolution thermodynamics for 1,3,5trichlorobenzene in organic solvents. J. Chem. Eng. Data 2016, 61, 380−390. (19) Chen, X. Y.; Zhan, S. Y.; Chen, Y. F.; Jin, Y. X.; Zeng, L. L.; Zhao, J.; Li, R. R.; Han, D. M. Solubility Measurement and Modeling of 1-(3-nitrophenyl) Ethanone and 1-(4-nitrophenyl) Ethenone in Nine Pure Organic Solvents from T = (278.15 to 318.15) K and Mixing Properties of Solutions. J. Chem. Eng. Data 2018, 63, 2875− 2887. (20) Smallwood, I. M. Handbook of organic solvent properties; Amoled: London, 1996. (21) Rosenbrock, H. H. An automatic method for finding the greatest or least value of a function. Comput. J. 1960, 3, 175−184. (22) Smith, J. M.; Van Ness, H. C.; Abbott, M. M. Introduction to Chemical Engineering Thermodynamics; McGraw-Hill: New York, 2001. (23) Cong, Y.; Wang, J.; Du, C. B.; Han, S.; Meng, L.; Zhao, H. K. Solubility determination and thermodynamic modeling of 5-nitro-8hydroxyquinoline in ten organic solvents from T = (278.15 to 313.15) K and mixing properties of solutions. J. Chem. Thermodyn. 2016, 100, 60−71.

AUTHOR INFORMATION

Corresponding Authors

*Tel.: +86 576 85486698. Fax: +86 576 85137169. E-mail: [email protected] (R.L.). *Tel.: +86 576 85486698. Fax: +86 576 85137169. hdm@tzc. edu.cn (D.H.). ORCID

Rongrong Li: 0000-0001-6112-6203 Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The project was supported by the Science and Technology Plan Project in Zhejiang Province (Grants 2016C37040 and 2015C33224), the State Key Laboratory of Chemical Resources Engineering under Grant CRE-2012-C-303, and the National Natural Science Foundation of China (Grants 21506138, 21375092, and 21575097).

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Solubility Determination and Thermodynamic Modeling of Buprofezin

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