Solubility and Solvent Effect of Acetamiprid in Thirteen Pure Solvents

Jul 18, 2019 - The experimental solubility data in pure solvents were correlated through the Apelblat equation, while those in liquid mixtures through...
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Article Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Solubility and Solvent Effect of Acetamiprid in Thirteen Pure Solvents and Aqueous Solutions of Ethanol Xi Zhao,† Ali Farajtabar,‡ Hongkun Zhao,*,† and Gui Han*,† †

College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, People’s Republic of China Department of Chemistry, Jouybar Branch, Islamic Azad University, Jouybar 4776186131, Iran

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‡

ABSTRACT: The determination of solubility of acetamiprid dissolved in thirteen pure solvents such as isobutanol, methanol, ethanol, n-butanol, isopropanol, acetone, ethylene glycol, 1-methyl-2-pyrrolidinone, ethyl acetate, dimethyl sulfoxide (DMSO), 1,4-dioxane, N,N-dimethylformamide, and water and binary liquid mixtures (ethanol + water) was carried out using the shake-flask method at the temperatures from 278.15 to 318.15 K under local atmospheric pressure of 101.2 kPa. The observed values of mole fraction solubility were the highest in DMSO and the lowest in water. A linear solvation energy relationship analysis was carried out to reveal how much and what type of intermolecular solvent−solvent and solute−solvent interactions were responsible for the solubility variation in these thirteen pure solvents. The results exhibited that the solubility of acetamiprid in these thirteen monosolvents depends significantly upon the Hildebrand parameter and nonspecific dipolarity/polarizability interactions of the solvents. The experimental solubility data in pure solvents were correlated through the Apelblat equation, while those in liquid mixtures through the Apelblat−Jouyban−Acree model, the van’t Hoff−Jouyban−Acree model, and the Jouyban−Acree model. For the selected pure solvents, the largest values of relative average deviation and root-mean-square deviation were, respectively, 1.77% and 36.21 × 10−4 and for the mixtures were 5.15% and 4.81 × 10−4, respectively. In the ethanol + water mixtures, the log x12 values positively deviated from the average ones of log x12, which showed that the acetamiprid was preferentially solvated by ethanol.

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Lepidoptera, Hemiptera, and Coleoptera families.6−9 Although a lot of investigations have been made on this class of pesticides, many researchers have mainly focused on their synthesis and application.10−15 The information about the solubility of acetamiprid in common solvents is scarce in literatures. Till date, the solubility of acetamiprid in only water and aqueous systems consisting of sodium dicarbamidochlorate, monoethanolamine acetate, and ethanol has been reported.6,16−18 Acetamiprid has the water solubility of 4.25 g L−1 at 298 K,16,17 which may influence its biological activity.19,20 With the purpose of improving its aqueous solubility, lot of methods such as aqueous ionic liquid systems and solid solubilization/dispersion have been employed in the published works.21,22 These techniques necessitate many exact solubility values in solvent mixtures and pure solvents. In this regard, it is very important to know the solubility of acetamiprid in solvent mixtures and pure solvents, which may present a comprehensive description for a lot of thermodynamic functions, mechanisms, and physicochemical properties relating to the physicochemical stability of pharmaceutical dissolutions. Based on the above considerations, this work mainly reports the solubility of acetamiprid in several commonly used

INTRODUCTION Solubility of a drug in pure solvents and solvent mixtures is of great significance for designing pharmaceutical products and obtaining complete information about the physicochemical property of the drug dissolutions.1−5 In addition, knowledge of a solute’s solubility in solvents is needed to confirm appropriate solvents for extraction, production, separation, and purification of organic compounds.3,4 A lot of solubility models have been employed to predict and correlate drug solubility in different pure solvents and mixed solutions, which can shorten the time and reduce the cost in solubility determination.3 The dependence of solid solubility upon temperature also permits us to perform thermodynamic investigation to obtain information related to the mechanism of the solid dissolution process.5 The neonicotinoids constitute the fastest developing class of pesticides after pyrethroids. Acetamiprid, whose IUPAC name is (E)-N1-[(6-chloro-3-pyridyl)methyl]-N2-cyano-N1-methylacetamidine (Figure 1, CAS Reg. No. 135410-20-7), is a neonicotinoid pesticide with extreme activity that has been widely employed in controlling the insects of Thysanoptera,

Received: April 4, 2019 Accepted: July 5, 2019

Figure 1. Chemical structure of acetamiprid. © XXXX American Chemical Society

A

DOI: 10.1021/acs.jced.9b00294 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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0.996 0.996 0.997 0.995 0.994 0.995 0.996 0.993 0.995 0.995 0.996 0.994 0.994 conductivity < 2 μS cm−1 crystallization none none none none none none none none none none none none distillation our lab

a

222.67 32.04 46.07 60.10 60.10 74.12 58.08 62.07 99.13 88.11 78.13 88.11 73.10 18.02 acetamiprid methanol ethanol isobutanol isopropanol n-butanol acetone EG NMP ethyl acetate DMSO 1,4-dioxane DMF water

High-performance liquid phase chromatography. bGas chromatography.

analytical method final mass fraction purity source molar mass g mol−1

CAS Reg. no.

0.983 0.996 0.995 0.995 0.996 0.994 0.995 0.993 0.996 0.995 0.996 0.994 0.996

purification method B

chemicals

Table 1. Detailed Information on the Materials Used in This Work

initial mass fraction purity

EXPERIMENTAL SECTION Drug and Reagents. Raw acetamiprid was acquired from “Suzhou Jingye Medicine & Chemical Co., Ltd., China”, with the mass fraction purity of 0.983. The purification of the crude raw material was carried out via crystallization in pure ethanol. Fifty milliliters of pure ethanol was added into a flask containing about 15 g of raw acetamiprid. The mixture was heated to about 340 K and then cooled slowly to room temperature (about 290 K). The pure acetamiprid precipitated, leaving impurities dissolved in ethanol. Vacuum filtration was used to isolate the crystals. This purification process was repeated three times. The final composition of acetamiprid was 0.996 in mass fraction, which was analyzed via the Agilent1260 high-performance liquid phase chromatography (HPLC). Isobutanol, methanol, acetone, ethanol, n-butanol, isopropanol, EG, NMP, ethyl acetate, DMSO, 1,4-dioxane, and DMF were purchased from “Sinopharm Chemical Reagent Co., Ltd., China” and used directly without further treatment. The mass fractions of the selected organic solvents were analyzed through gas chromatography (GC Smart-2018) and were found to be no less than 0.993. Distilled water was obtained from our laboratory, and its conductivity was no greater than 2 μS cm−1. More details on these substances used in the experiment are given in Table 1. Solubility Determination. The masses of solvent, saturated liquid, and solute were decided through an analytical balance of CPA225D model, which had a standard uncertainty of 0.0001 g. The temperature of all investigated systems was regulated through a thermostatic water bath QYHX-1030 model provided by Shanghai Joyn Electronic CO., Ltd., China. The standard uncertainty of the water bath did not exceed 0.05 K. The equilibrated solutions of acetamiprid dissolved in pure solvents and ethanol + water mixtures were achieved via a shake-flask technique, which had been widely employed in earlier works.23−25 Prior to the experiments, the verification of the apparatus reliability was carried out via determining the benzoic acid solubility in pure solvent of toluene.23 The composition of acetamiprid in equilibrated liquid was determined by using the Agilent-1260 HPLC. The solutions of acetamiprid in pure and ethanol + water mixtures were prepared via the analytical CPA225D balance. All of the experiments were carried out under ambient pressure (101.2 kPa). Nearly 15 mL of pure solvent or mixed solvents was placed in a 25 mL flask for each experiment. After the solution was mixed entirely, the solution in the flask was

Suzhou Jingye Medicine & Chemical Co., Ltd., China Sinopharm Chemical Reagent Co., Ltd., China

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135410-20-7 67-56-1 64-17-5 78-83-1 67-63-0 71-36-3 67-64-1 107-21-1 872-50-4 141-78-6 67-68-5 123-91-1 68-12-2 7732-18-5

monosolvents and binary solvent mixtures. From a lot of commonly solvents used in industry, we selected thirteen pure solvents, e.g., isobutanol (IUPAC name: 2-butanol), methanol, n-butanol (IUPAC name: 1-butanol), ethanol, isopropanol, acetone, ethylene glycol (EG; IUPAC name: ethane-1,2-diol), 1-methyl-2-pyrrolidinone (NMP; IUPAC name: 1-methylpyrrolidin-2-one), ethyl acetate, dimethyl sulfoxide (DMSO), 1,4dioxane, N,N-dimethylformamide (DMF), and water and binary mixtures of ethanol + water. Accordingly, the goals of the present study were to determine the solubility of acetamiprid in the 13 monosolvents and ethanol + water mixtures from (278.15 to 318.15) K and to describe mathematically the obtained solubility values by using several solubility models. The reason for choosing the ethanol + water mixture in this paper is that the ethanol + water mixture is employed as a solvent in not only the reaction process10−12 but also practical applications.13−15

HPLCa GCb GC GC GC GC GC GC GC GC GC GC GC conductivity meter

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DOI: 10.1021/acs.jced.9b00294 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

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Figure 2. XRD patterns of acetamiprid (a) equilibrated with methanol; (b) equilibrated with isobutanol; (c) equilibrated with isopropanol; (d) equilibrated with n-butanol; (e) equilibrated with acetone; (f) equilibrated with EG; (g) equilibrated with NMP; (h) equilibrated with ethyl acetate; (i) equilibrated with DMSO; (j) equilibrated with 1,4-dioxane; (k) equilibrated with DMF; (m) raw material; (n) equilibrated with ethanol; (o) equilibrated with water; and (p) equilibrated with ethanol (1) + water (2) mixture.

Table 2. Experimental Mole Fraction Solubility (x) of Acetamiprid in Different Monosolvents at the Temperature Range from T = 278.15 to 318.15 K under 101.2 kPaa T (K) 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

103 x

100 RD

Methanol 19.88 3.62 22.69 −1.60 27.30 −0.84 32.48 −0.58 38.16 −1.07 45.23 −0.02 53.24 0.83 61.85 0.91 70.30 −0.69 acetone 103.6 3.50 117.7 −0.71 137.9 −1.46 162.0 -1.52 190.5 −1.01 226.3 0.79 263.7 1.09 303.0 0.32 346.5 −0.54

103 x

100 RD

Ethanol 16.24 1.74 19.21 −1.47 23.17 −1.43 28.44 1.59 32.83 −0.36 38.17 −0.52 44.77 1.23 49.99 −0.97 57.23 0.24 EG 9.784 5.38 10.64 −5.61 13.41 −1.01 16.26 0.22 19.41 0.51 23.04 0.81 26.90 0.02 31.34 −0.46 36.71 0.10

103 x

100 RD

Ethyl Acetate 10.60 4.04 12.77 −0.03 15.48 −2.12 19.03 −1.66 23.35 −0.12 28.07 0.45 33.24 0.45 39.01 0.62 44.78 −0.51 n-Butanol 1.490 4.27 1.647 −3.95 2.017 −1.13 2.415 0.05 2.840 0.17 3.369 1.71 3.780 −1.63 4.472 0.83 5.072 −0.26

103 x

100 RD

DMF 175.5 2.92 200.5 −0.03 229.2 −2.41 268.5 −1.80 317.6 0.37 368.5 1.04 421.0 0.64 476.9 −0.17 541.9 −0.25 NMP 196.7 3.32 221.4 −0.99 254.9 −2.39 299.4 −1.21 352.4 0.70 404.6 0.70 460.4 0.30 522.8 0.15 589.0 −0.32

103 x

100 RD

Isobutanol 2.803 3.22 3.151 −2.10 3.705 −2.47 4.521 1.35 5.195 −0.38 6.133 0.98 6.964 −1.05 8.205 0.91 9.316 −0.36 DMSO

375.8 425.6 481.2 539.6 608.3 679.9

1.51 −1.50 −1.36 1.10 0.71 −0.49

103 x

100 RD

Isopropanol 6.704 3.12 7.627 −1.39 8.862 −3.19 10.78 0.37 12.68 1.08 14.71 1.04 16.57 −1.48 19.49 0.79 22.06 −0.24 1,4-Dioxane

69.32 79.90 94.14 113.2 132.3 153.5 175.2

103 x

100 RD

Water 0.1458 5.83 0.1735 0.23 0.2134 −1.75 0.2685 −1.24 0.3476 −1.62 0.4500 −0.03 0.5721 1.08 0.7205 0.62 0.9107 −0.51

2.22 −1.32 −1.82 0.36 0.54 0.57 −0.42

a

Standard uncertainties u are u(T) = 0.02 K and u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.032.

was aqueous solutions of methanol in a volume ratio of 1:1 at a flow speed of 0.8 mL min−1. Each test was carried out thrice, and each sampling was carried out three times for a certain solution. The relative standard uncertainty was no more than 3.2% for mole fraction solubility. Characterization of Solid Phase. The solid and liquid phase equilibrium was obtained by performing filtration under negative pressure and then tested by X-ray powder diffraction (XRD) to illustrate polymorphic transformation or solvate formation of acetamiprid during the experiment. XRD was carried out on a Bruker AXS D8 instrument through a Cu Kα radiation with a wavelength of 1.54184 nm at barometric conditions. The scan speed was set to 5° min−1. The tube voltage and tube current were set to 40 kV and 30 mA, respectively. The data (2θ) were gathered from 5 to 80°.

transferred to a thermostatic mechanical shaker provided by Tianjin Ounuo Instrument Co. Ltd., China. The system was shaken via the mechanical shaker at the speed of 150 rpm in experimental temperature. To get the equilibration time of the investigated systems, around 0.5 mL of liquor was withdrawn through a 2 mL syringe attached to a PTFE filter (0.2 μm) every 1 h and analyzed using the HPLC. The results indicated that it took 15 h for all of the studied systems to be equilibrated. Once the systems were had been equilibrated, the solutions were kept static at experimental conditions to allow any solid to precipitate from the solutions. The upper liquid phase was withdrawn via a 2 mL syringe preheated or precooled and put rapidly into a 25 mL volumetric flask. Then, the sample (diluted if necessary) was tested through an Agilent-1260 HPLC. Analysis. The acetamiprid composition in an equilibrium liquor was evaluated by the HPLC test. A reverse-phase column (LP-C18, 250 mm × 4.6 mm) was employed in the experiment at temperature close to 303 K. The wavelength of the UV−vis detector was set at 254 nm.26 The mobile phase

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RESULTS AND DISCUSSION XRD Diffraction. The XRD patterns of the raw material acetamiprid and the solid equilibrated with liquid phase in pure solvents and ethanol + water solutions are shown in Figure 2.

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Figure 3. Mole fraction solubility (xexp) of acetamiprid in different monosolvents at studied temperatures: ⧫, methanol; ◀, ethanol; ▶, isopropanol; ★, n-butanol; □, isobutanol; ○, EG; ◊,water; Δ, 1,4-dioxane; ▽, acetone; ☆, ethyl acetate; ■, DMF; ▲, NMP; and ▼, DMSO. , Calculated curves from the Apelblat equation.

0.2438× 10−3 reported by Shukurov and co-workers.18 It should be noted that Shukurov and co-workers determined the solubility of acetamiprid at 272 K. The equilibrated solid is a mixture of acetamiprid and ice, not pure acetamiprid. With the intention of getting more details on the modes of intermolecular interactions contributing to the determined solubility, a multiple linear regression analysis (MLRA) is carried out to relate solvent effects to several solvent descriptors. In this regard, linear solvation energy relationships concept, LSER, offers a well-known approach that describes the total change in the Gibbs free energy (XYZ) as a sum over contributions from individual solute−solvent and solvent− solvent interactions in the form of eq 1.27,28

As may be observed, all of the XRD scans of solids equilibrated with the corresponding liquid phases have similar characteristic peaks as that of the raw acetamiprid. Accordingly, no polymorphic transformation or solvate formation took place in the experiment. Solubility in Monosolvents. The determined solubility of acetamiprid in isobutanol, methanol, EG, ethanol, n-butanol, isopropanol, acetone, NMP, ethyl acetate, DMSO, 1,4-dioxane, DMF, and water from 278.15 to 318.15 K are listed in Table 2 and also plotted in Figure 3. The solubility of acetamiprid in these pure solvents increases with increasing temperature. The solubility value is observed to be smallest in water and highest in DMSO. The solubility values in the 13 pure solvents follow the trend of DMSO > NMP > DMF > acetone > 1,4-dioxane > methanol > ethanol > ethyl acetate > EG > isopropanol > isobutanol > n-butanol > water. The solubility of acetamiprid in water is 4.25 g L−1 at 298 K.16,17 Here, the density of the aqueous solution of acetamiprid is considered to be same as that of pure water at 298 K. In this manner, the reported solubility value is converted to the mole fraction, which is 0.3453 × 10−3 at 298 K and is plotted in Figure 4 as well as that determined by us for comparison. As

XYZ = XYZ0 + cavity formation energy +

∑ solvent

− solute interaction energy

(1)

For a given solute in a variety of solvents, XYZ0 is a constant that depends just on the solute’s properties. Cavity formation energy is the amount of work that needs to be done to break cohesive interactions in the solvent for making voids for the solute’s accommodation and thus considers contribution from solvent−solvent interactions. This term can be expressed as the product of Vs and the square of δH; Vs is the molar volume of the solute in liquid phase; δH stands for the Hildebrand solubility parameter that is equal to the square root of the cohesive energy density in the solvent. The last term on the right-hand side in eq 1 considers the energy contribution from all the possible solute−solvent interactions to the total change in the Gibbs free energy. These energy terms can be expressed as a function of Kamlet, Abboud, and Taft parameters, KAT, by which the relative potential of the solvent to participate in different types of interactions is parameterized via α, π*, and β scales, respectively.26 The parameter α denotes the hydrogen bond acidity, π* is the dipolarity−polarizability, and β denotes the hydrogen bond basicity of the solvent. Accordingly, eq 1 is rewritten in the form of KAT-LSER as eq 2 to relate the Gibbs free energy of the solvent-dependent process to examine the impact of different types of solute−solvent and solvent− solvent interactions on the solvent effect.29

Figure 4. Solubility of acetamiprid in water determined in this work and that reported in previous publications: ■, this work; ●, refs 16 and 17; ▲, ref 18.

seen in Figure 4, the mole fraction solubility of acetamiprid in water at 298.15 K is determined in this work to be 0.3476 × 10−3, which is very close to 0.3453 × 10−3 reported by Coscollà and Raina-Fulton.16,17 The little difference is within the allowable range of deviation. Nevertheless, the solubility of acetamiprid in water at a relative low temperature of 272 K determined by extrapolation in this study is lower than

2 ji V δ zy ln(xi) = c0 + c1π * + c 2β + c3α + c4jjj s H zzz j 100RT z k {

(2)

where ln(xi) is the natural log of the mole fraction solubility that is proportional to the Gibbs free energy of solubility (ΔG) D

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ΔG

ln(x) = −5.13(1.73) + 0.36(1.62)α − 0.87(2.21)β 2 ji V δ zy + 8.25(2.95)π * − 6.60(2.40)jjj s H zzz j 100RT z k {

by the expression ln xi = − RT , herein R and T are the gas constant and temperature, respectively; c0 is the hypothetical value of ln(xi) when α = β = π* = δH = 0; ci=1−3 show the relative impact of the corresponding solvent property on the solubility; and c4 gives the sensitivity of solubility variation in a solvent−solvent interaction. It is worthy noting that the last term on the right-hand side of eq 2 is divided by 100RT to make it dimensionless and comparable with other presented terms. KAT-LSER model was used to gain details about the solvent effect on the solubility of acetamiprid in pure solvents at 298.15 K. The values of α, β, π*, and δ2H for these pure solvents are cited in literatures30,31 and presented in Table 3. The molar volume of acetamiprid, Vs = 189.6 cm3 mol−1, is obtained from the Scifinder database.32

n = 13, R2 = 0.84, RSS = 8.56, and F = 10.37. The R2 is relatively small. So, we try the MLRA of ln x with the exception of methanol and ethanol. The correlation result is described in eq 4. ln(x) = −5.39(1.14) − 1.05(1.14)α − 0.22(1.47)β ij V δ 2 yz + 7.55(1.95)π * − 5.36(1.61)jjj s H zzz j 100RT z k {

α

β

π*

δH (J cm−3)1/2

methanol ethanol ethyl acetate DMF isobutanol isopropanol water acetone EG n-butanol NMP DMSO

0.98 0.86 0 0 0.79 0.76 1.17 0.08 0.9 0.84 0 0

0.66 0.75 0.45 0.69 0.84 0.84 0.47 0.43 0.52 0.84 0.77 0.76

0.6 0.54 0.55 0.88 0.4 0.48 1.09 0.71 0.92 0.47 0.92 1

29.61 26.52 18.48 24.86 22.66 23.58 47.82 19.95 33.11 23.20 22.96 26.68

(4)

n = 11, R2 = 0.95, RSS = 2.75, and F = 27.36. where R2, F, and RSS denote the correlation coefficient, the F-test, and the residual sum of squares, respectively. The standard deviation for each coefficient is presented by the value in parentheses. A detailed inspection of eq 4 reveals that the coefficient for both of α and β is accompanied by high unaccepted standard deviation. In addition, the negative values obtained for these terms are not consistent with the expectation of solute−solvent interactions that have a positive effect on the solubility. Thus, deletion of α and β from the model results in a KAT-LSER equation, eq 5, that offers a satisfied correlation consequence for the solubility of acetamiprid in pure solvents.

Table 3. Hildebrand Solubility Parameters (δH) and Solvatochromic Parameters α, β, and π* for the Selected Solvents solvent

(3)

ln(x) = −6.37(0.67) + 9.11(1.10)π * − 6.66(0.64) ij Vsδ H2 yz jj zz jj zz 100 RT k {

(5)

R2 = 0.93, n = 11, RSS = 3.49, and F = 56.64. Equation 5 explains 93% of the variation in the solubility and reveals that the dipolarity−polarizability and cavity terms are the main contributors to the solvent effect in the studied solvents. The effect of specific hydrogen-bonding solute− solvent interactions is not significant with respect to other intermolecular interactions. The obtained coefficients for the cavity term and dipolarity−polarizability are 6.66 and 9.11, respectively. The relative sensitivity from each solvent’s descriptor to the solvent effect can be readily determined by 100ci the expression . Therefore, the solubility of acetamiprid is

In practice, experimental values for ln(xi) are fitted to eq 2 by multiple linear regression analysis, MLRA, implemented using the least-squares fitting function LINEST in Excel program. In this procedure, the sum of square of residuals (difference between experimental ln x values and those predicted by eq 2 over the full composition ranges containing 11 data points) is minimized during an iterative process by varying the values of regression coefficients ci=0−4. The results of MLRA for the solubility of acetamiprid is described in eq 3 for all of the pure solvents.

∑ ci

Table 4. Experimental Mole Fraction Solubility (103xT,We) of Acetamiprid in Mixed Solvent of Ethanol (w) + Water (1 − w) with Different Mass fractions within the Temperature Range from T = (278.15 to 318.15) K under 101.2 kPaa W T (K)

0

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15

0.1458 0.1735 0.2134 0.2685 0.3476 0.4500 0.5721 0.7205 0.9107

0.4677 0.6114 0.7684 0.9756 1.213 1.484 1.805 2.168 2.604

0.9471 1.240 1.582 2.034 2.496 3.058 3.728 4.443 5.195

1.533 1.984 2.514 3.237 4.088 4.985 6.116 7.466 8.965

2.265 3.025 3.831 4.824 6.065 7.414 8.856 10.49 12.28

3.248 4.311 5.338 6.655 8.171 9.982 12.08 14.11 16.98

4.345 5.634 7.430 8.901 10.59 12.76 15.39 18.02 21.30

6.127 8.003 10.24 12.33 14.27 16.85 19.43 22.99 26.63

8.382 10.79 13.72 16.28 18.56 21.91 25.20 28.85 33.19

11.76 14.77 17.85 21.21 24.71 28.56 32.61 38.36 44.52

16.24 19.21 23.17 28.44 32.83 38.17 44.77 49.99 57.23

a

Standard uncertainties u are u(T) = 0.02 K and u(p) = 0.45 kPa. Relative standard uncertainty ur is ur(x) = 0.032. Solvent mixtures were prepared by mixing different masses of the solvents with relative standard uncertainty ur(w) = 0.0002. w represents the mass fraction of methanol in mixed solvents of ethanol (w) + water (1 − w). E

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where A, B, and C refer to the equation parameters. The Jouyban−Acree model is expressed as eq 7.23,36

sensitive by 42% to the cavity term and 58% to the dipolarity− polarizability of the solvent. It means that the effect of dipolarity−polarizability is 1.37 times larger than the cavity term. This result is in accordance with the nature of acetamiprid. Molecular structure in Figure 1 indicates that acetamiprid is a polar and a high polarizable compound due to the presence of number of nitrogen atoms and chlorine atoms for which the lone pair of electrons are unsymmetrically distributed along the relatively large-size structure of the molecule. Therefore, it is not unexpected that acetampirid participates favorably in nonspecific long-range electrostatic interactions with the solvent. As expected, the negative coefficient of the cavity term indicates that the solubility of acetamiprid decreases with increasing Hildebrand solubility parameter of the solvents. The π* coefficient is shown to be positive, so the solubility of acetamiprid increases with increasing polarizability/dipolarity of the solvents. Solubility in Mixed Solvents. The mole fraction solubility of acetamiprid in the ethanol + water solution from 278.15 to 318.15 K with different mass fractions of ethanol is presented in Table 4. In addition, the dependence of the solubility of acetamiprid upon ethanol composition and temperature is plotted in Figure 5. It exhibits that in the

ln x12 = w1 ln x1, T + w2 ln x 2, T +

w1w2 T /K

2

∑ Ji (w1 − w2)i i=0

(7)

In eq 7, x12 denotes the mole fraction solubility of acetamiprid in the ethanol + water solution; w1 and w2 refer to the mass fraction of ethanol and water in the ethanol + water mixture free of acetamiprid, respectively; and x1,T and x2,T are the solubility of acetamiprid in pure solvents, respectively. Ji denotes the model parameters. By combining the van’t Hoff equation and eq 7, the van’t Hoff−Jouyban−Acree equation is obtained as in eq 8, where A and B are parameters of the van’t Hoff equation. i i B1 yz B2 yz zz + w2jjjA 2 + zz ln x12 = w1jjjjA1 + z j T T /K /K z{ k { k 2 ww + 1 2 ∑ Ji (w1 − w2)i T /K i = 0

(8)

In the similar manner, by introducing eqs 6 and 7, the Apelblat−Jouyban−Acree model (eq 9) is acquired.23,36 ÅÄÅ ÑÉÑ B1 Å Ñ ln x12 = w1ÅÅÅA1 + + C1 ln(T /K)ÑÑÑ ÅÅÇ ÑÑÖ T /K ÄÅ ÉÑ ÅÅ ÑÑ B2 + w2ÅÅÅA 2 + + C2 ln(T /K )ÑÑÑ ÅÇÅ ÑÖÑ T /K 2 ww + 1 2 ∑ Ji (w1 − w2)i T /K i = 0 (9) The solubility of acetamiprid in the 13 pure solvents and the ethanol + water mixture is described mathematically through eqs 6−9 with MathCAD software. The objective function is expressed as F=

Figure 5. Mole fraction solubility (x) of acetamiprid in ethanol (w) + water (1 − w) mixed solutions with different mass fractions at different temperatures: w, mass fraction of ethanol; ☆, w = 1; Δ, w = 0.9000; ○, w = 0.8000; □, w = 0.7000; ★, w = 0.6000; ◊, w = 0.5000; ⧫, w = 0.4000; ▼, w = 0.3000; ▲, w = 0.2000; ●, w = 0.1000; ■, w = 0; and , calculated curves by the Jouyban−Acree model.

∑ (ln xie − ln xic)2

(10)

i=1

Additionally, the relative average deviation (RAD), root mean square deviation (RMSD), and relative deviation (RD) are also obtained through eqs 11−13, respectively. RAD =

ethanol + water mixture, the solubility of acetamiprid increases with increase in temperature and ethanol composition. The maximum solubility of acetamiprid is found in pure ethanol. Solubility Modeling. In order to mathematically describe the solubility of acetamiprid in the 13 pure solvents and ethanol + water solutions, the Apelblat equation33−35 is used to correlate the solubility of acetamiprid in the 13 pure solvents; and Jouyban−Acree model,23,36 combination of Jouyban− Acree model with Van’t Hoff equation23,36 and combination of Jouyban−Acree model with Apelblat equation,23,36 in ethanol + water mixture. The dependence of solubility of acetamiprid (xT) upon temperature T/K in pure solvents is expressed via the Apelblat equation (eq 6).33−35 B ln xT = A + + C ln T (6) T

1 N

i |xic − xie| yz zz zz e x i k {

∑ jjjjj

(11)

N

RMSD = RD =

∑i = 1 (xic − xie)2 N

(12)

xie − xic xie

(13)

xci

where N is to the data number, is the calculated solubility of acetamiprid, and xei is the experimental value. The regressed values of parameters A, B, and C in the Apelblat equation as well as the RMSD and RAD are listed in Table 5; the parameters in the Jouyban−Acree, van’t Hoff− Jouyban−Acree, and Apelblat−Jouyban−Acree models together with the RAD and RMSD values are given in Table 6. Moreover, the back-computed solubility of acetamiprid in the 13 pure solvents via the Apelblat equation is shown graphically F

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x12) and the solvent composition is linear. The deviation from the ideal mixture is expressed as

Table 5. Parameters’ Values of the Modified Apelblat Equation, RAD, and RMSD Values for Acetamiprid in Different Monosolvents solvent

A

B

C

100 RAD

methanol ethanol isobutanol isopropanol n-butanol acetone EG NMP ethyl acetate DMSO 1,4-dioxane DMF water

12.754 139.419 −15.402 16.446 30.585 −24.653 8.618 21.253 121.971 −21.586 52.192 8.911 −199.16

−3171.492 −8742.18 −1879.86 −3230.21 −4012.98 −1329.23 −3149.78 −3124.50 −8382.03 −933.664 −4931.94 −2629.89 4912.01

−0.943 −19.923 2.887 −1.754 −4.035 4.820 −0.351 −2.075 −17.132 4.188 −6.668 −0.218 30.668

1.13 1.06 1.44 1.41 1.57 1.22 1.57 1.12 1.10 0.10 1.04 1.07 1.77

104 RMSD 4.30 3.47 0.68 1.72 0.45 22.15 2.83 36.21 2.44 7.38 10.92 34.16 0.05

δ = [log x12 − (xs1 log x1 + xs2 log x 2)] /[log x1 − log x 2] (14)

here x1 and x2 are the mole fraction solubility of acetamiprid in the pure ethanol and pure water, respectively. xs1 and xs2 are to mole fractions of pure ethanol and pure water in acetamipridfree mixtures. δ values at 298.15 K for ethanol (1) + water (2) solutions are presented in Table 7, and the dependence of δ values upon xs1 is given in Figure 6. The positive δ values are maximum with ethanol composition xs1 < 0.5.

Table 6. Values of Parameters Obtained Using Thermodynamic Cosolvency Models Jouyban−Acree parameter J0 J1 J2

RAD 102 RMSD 104

Van’t Hoff−Jouyban− Acree

Apelblat−Jouyban− Acree

value

parameter

value

parameter

value

997.32 −1041.79 733.10

A1 B1 A2 B2 J0 J1 J2

5.7538 −2737.19 5.9392 −4082.56 903.03 −879.38 497.38

A1 B1 C1 A2 B2 C2 J0 J1 J2

139.391 −8740.23 −19.9186 98.2853 −8255.70 −13.750 909.54 −881.68 513.67 4.24 3.98

3.95 4.81

5.15 4.42

Figure 6. Plot of δ as a function of ethanol composition for solvent mixtures of ethanol (1) + water (2).

Preferential Solvation of Acetamiprid. For the ethanol (1) + water (2) mixtures, log x1 > log x12 > log x2, with the component 1 being ethanol. As a result, the plot of log x12 vs xs1 does not show a maximum value. If the local composition of the solvent i (xsLi ) around the solute is different from the average one, the variation of the nonlinear log x12 with ethanol composition is caused by preferential solvation of the solute.23 xsLi may be obtained by39,40 log x12 = xs1L log x1 + xs2L log x 2

in Figure 3; and in the ethanol + water mixture via the Jouyban−Acree model, in Figure 5. For the selected pure solvents, the RMSD value is the highest for acetamiprid + DMF mixture (36.21 × 10−4), while the RAD values are no more than 1.77%. For the ethanol + water mixture, the values of RAD and RMSD achieved via the Jouyban−Acree model are 3.95% and 4.81 × 10 −4 , respectively; the van’t Hoff−Jouyban−Acree model are 5.15% and 4.42 × 10−4, respectively; and the Apelblat− Jouyban−Acree model are 4.24% and 3.98 × 10−4, respectively. Overall, the selected models may present satisfactory results for the solubility of acetamiprid in the 13 pure solvents and the ethanol + water mixture at the temperatures studied. For an ideal solution, the standard Gibbs energy can be obtained through the average value of the mole fraction of the solute.37,38 The relationship between the solute solubility (log

By using the relation xs1L =

xsL1

+

xsL2

(15)

= 1, one may acquire

log x12 − log x 2 log x1 − log x 2

(16)

Equation 17 is attained through combining eqs 14 and 16. δ = xs1L − xs1

(17)

Accordingly, δ described as eq 14 stands for the deficit of solvent 1 in the local area. The achieved δ values are positive for the ethanol (1) + water (2) solution, which illustrate that an excess appears for ethanol in the local region nearby acetamiprid compared with that in the bulk region. As a result, acetamiprid is preferentially solvated by ethanol. This case maybe due to the breaking of water ordering round the polar groups of acetamiprid.

Table 7. Values of Log x12 and δ in Mixed Solvents of Ethanol (1) + Water (2) parameter xs1 log x12 δ Kps

value 0 −3.459 0 0

0.0417 −2.916 0.233 8.643

0.0891 −2.603 0.344 7.832

0.1436 −2.388 0.398 7.033

0.2068 −2.217 0.422 6.486

0.2812 −2.088 0.413 5.809 G

0.3698 −1.975 0.381 5.142

0.4772 −1.846 0.34 4.889

0.6101 −1.731 0.265 4.459

0.7788 −1.607 0.159 4.257

1 −1.484 0 0

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ORCID

Based on the above equations, the preferential solvation is usually described by Kps as eq 1839,41 K ps =

x1L(1

Ali Farajtabar: 0000-0002-5510-3782 Hongkun Zhao: 0000-0001-5972-8352

− x1)

x1(1 − x1L)

Notes

(18)

The authors declare no competing financial interest.

■

Kps may be regarded as an equilibrium constant, which refers to the following procedure solvent 1 + solvent 2(bound) ⇔ solvent 2 + solvent 1(bound)

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(19)

The “bound” denotes the solvent i in the local region. The values of Kps are calculated through xsLi , which is attained from the determined solubility data. The Kps values are tabulated in Table 7 and given in Figure 7. As may be shown, the values of Kps are dependent upon the solvent compositions of the ethanol (1) + water (2) solutions.

Figure 7. Plot of Kps as a function of ethanol composition for solvent mixtures of ethanol (1) + water (2).

■

CONCLUSIONS The solubility of acetamiprid in thirteen pure solvents and ethanol + water mixture was attained under about 101.2 kPa at temperatures from 278.15 to 318.15 K. The mole fraction solubility of acetamiprid in the 13 pure solvents increased with increasing temperature and followed the order of DMSO > NMP > DMF > acetone > 1,4-dioxane > methanol > ethanol > ethyl acetate > EG > isopropanol > isobutanol > n-butanol > water. Solvent effect analysis revealed that dipolarity−polarizability and cavity terms were the main factors contributing to variation in the solubility of acetamiprid. The determined solubility data in pure solvents were correlated by using the Apelblat equation. The maximum values of RAD and RMSD were 1.77% and 36.21 × 10−4, respectively. Moreover, the Jouyban−Acree model, Apelblat−Jouyban−Acree model, and van’t Hoff−Jouyban−Acree model were used for describing the solubility of acetamiprid in the ethanol + water solution obtaining the largest RMSD and RAD values of 4.81 × 10−4 and 5.15%, respectively. Solvation analysis in the binary ethanol + water solution revealed that nonideal behavior and solvent−solvent interaction played an important role in the solubility of acetamiprid. In ethanol + water solutions, acetamiprid presented preferential solvation; ethanol was preferred over water in for acetamiprid.

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REFERENCES

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (H.Z.). *E-mail: [email protected]. Tel: + 86 51487975244 (G.H.). H

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