o-Nitrophenylacetonitrile Solubility in Several Pure Solvents

Article pubs.acs.org/jced

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

o‑Nitrophenylacetonitrile Solubility in Several Pure Solvents: Measurement, Correlation, and Solvent Effect Analysis Hairong Wang,† Xincheng Wang,† Gaoquan Chen,‡ Ali Farajtabar,§ Hongkun Zhao,*,‡ and Xinbao Li*,† †

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School of Environmental & Municipal Engineering, North China University of Water Resources and Electric Power, Zhengzhou, He’nan 450011, People’s Republic of China ‡ 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 ABSTRACT: The o-nitrophenylacetonitrile solubilities in some pure solvents such as n-propanol, methanol, toluene, ethanol, isopropanol, acetonitrile, acetone, cyclohexane, ethyl acetate, n-butanol, 2-butanone, isobutanol, acetic acid, water, 1,4-dioxane, and ethylbenzene were determined via a shake-flask method at temperatures from 278.15 to 333.15 K under about 101.2 kPa. Good dissolution ability was found for o-nitrophenylacetonitrile in the organic solvents. The order of solubility magnitude from high to low, except for the solvents of ethyl acetate and 1,4-dioxane, was as follows: acetone > 2-butanone > acetonitrile > toluene > (acetic acid, ethylbenzene) > methanol > ethanol > n-propanol > isopropanol > nbutanol > isobutanol > cyclohexane > water. X-ray powder diffraction analysis was carried out to analyze the solids equilibrated with the corresponding liquor, indicating that no polymorphic transformation or solvate formation took place in the 16 solvents. The correlation of the determined solubility was performed via the Wilson model, Apelblat equation, nonrandom two-liquid model, and λh equation. Maximum root-mean-square deviation and relative average deviation were 49.66 × 10−4 and 4.97%, respectively. The Apelblat equation presented the best correlating results among these models. In addition, the solvent−solvent and solute−solvent interactions were investigated on the basis of the approach of the linear solvation energy relationship.

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size distribution, yield, and purity of products.10−12 In an attempt to obtain p-nitrophenylacetonitrile with sufficient purity, the information on thermodynamic solubility for pnitrophenylacetonitrile and o-nitrophenylacetonitrile dissolved in different solvents at elevated temperatures is needed. Recently, our research group reports the p-nitrophenylacetonitrile solubility in several neat solvents and solvent mixtures.13,14 However, no o-nitrophenylacetonitrile solubility have yet been reported in the previous works. Based on the considerations described above, the aims of the present work are to (1) determine the equilibrium solubility of o-nitrophenylacetonitrile in some commonly used solvents namely n-propanol, methanol, toluene, ethanol, isopropanol, acetonitrile, acetone, cyclohexane, ethyl acetate, n-butanol, 2butanone, isobutanol, acetic acid, water, 1,4-dioxane, and ethylbenzene at temperatures from 278.15 to 333.15 K; (2) mathematically describe the obtained solubility via different solubility models; and (3) analyze the solvent effect on solubility for o-nitrophenylacetonitrile dissolved in these solvents.

INTRODUCTION o-Nitrophenylacetonitrile (molar mass, 162.15 g mol−1; CAS Reg. No. 610-66-2; structure, Figure 1) is a significant

Figure 1. Chemical structure of o-nitrophenylacetonitrile.

intermediate widely used in the synthesis of pharmaceuticals, agricultural chemicals, and fine products.1−6 As a key nitrosubstituted phenylacetonitrile isomer, o-nitrophenylacetonitrile is often accompanied as an impurity during the pnitrophenylacetonitrile production in industry, which is produced via benzylcyanide nitration using sulfuric acid and nitric acid mixtures as nitration agents.1,7−9 The mole ratio of the nitrophenylacetonitrile isomers is dependent on the type of reaction conditions and nitrating agents. Therefore, o-nitrophenylacetonitrile should be separated from the isomer mixtures. It is well-known that solvent crystallization is a widespread operation unit in industry to obtain products with high purity. The solid solubility in different solvents is fairly significant in the solvent crystallization process, which influences the crystal © XXXX American Chemical Society

Received: March 18, 2019 Accepted: April 23, 2019

A

DOI: 10.1021/acs.jced.9b00243 J. Chem. Eng. Data XXXX, XXX, XXX−XXX

ÄÅ ÉÑ ÅÅ ÑÑ Λ12 Λ 21 Å ÑÑ Å ln γ1 = −ln(x1 + Λ12x 2) + x 2ÅÅ − Ñ ÅÅÇ x1 + Λ12x 2 x 2 + Λ 21x1 ÑÑÑÖ

Journal of Chemical & Engineering Data

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Article

SOLUBILITY MODELS The equilibrium solubility of o-nitrophenylacetonitrile in the selected pure solvents was described mathematically using the Apelblat,13,15−18 λh,13,15−18 Wilson,13,15−18 and nonrandom two-liquid (NRTL) models13,15−18 so as to spread the usage of the obtained data. Also, the Kamlet−Taft linear solvation energy relationship (LSER)19 was used to analyze the solvent effect on solubility for o-nitrophenylacetonitrile dissolved in neat solvents. Apelblat Equation. It is a semiempirical equation and is suitable for mathematically describing both polar and nonpolar systems. The mole fraction solubility of a solid in neat solvents may be described via the Apelblat equation expressed as13,15−18 B ln x = A + + C ln T (1) T here x refers to the solubility of o-nitrophenylacetonitrile in a mole fraction in the studied solvents. A, B, and C are equation parameters. A and B exhibit the change in activity coefficient of a mixture, which can provide an indication of the effect of nonideal solution on the solute solubility, and C displays the fusion enthalpy dependence on temperature. Buchowski−Ksiazaczak λh Equation. The Buchowski− Ksiazaczak λh equation expressed as eq 2 is put forward by Buchowski and co-workers so as to investigate the solvent activity along a saturation line and the equilibrium solubility of the hydrogen bonding solid.13,15−18 This equation is another one to mathematically describe the liquid−solid equilibrium of o-nitrophenylacetonitrile in different solvents. É ÅÄÅ ij 1 λ(1 − x) ÑÑÑÑ 1 yzz Å lnÅÅÅ1 + ÑÑ = λhjjj − z j ÅÅÇ Ñ x Tm zz{ ÑÖ (2) kT The equation parameters are denoted as λ and h. Tm/K refers to the fusion temperature of o-nitrophenylacetonitrile. The parameters λ and h relate to the nonideality and excess enthalpy of a solution. Wilson Model. For an equilibrated liquid−solid system at a fixed pressure and temperature, based on the traditional theory of phase equilibrium, the solid solubility in solvents is described as shown in eq 3.

ÄÅ ÉÑ ÅÅ ÑÑ Λ 21 Λ12 Å ÑÑ ln γ2 = −ln(x 2 + Λ 21x1) + x1ÅÅÅ − Ñ ÅÅÇ x 2 + Λ 21x1 x1 + Λ12x 2 ÑÑÑÖ

(5)

Λ12 =

Λ 21 =

(8)

(9)

Gji = exp( −αjiτji)

(10)

αij = αji

(11)

τij =

Δgij (12)

RT

where Δgij refers to the interaction parameters that relate to the interaction energy and are believed to be a constant. Parameter α discloses the nonrandomness of the mixture. Let us assume that for the NRTL and Wilson models, the model parameter dependence upon temperature is linear,14,16 Λij and τij in the two equations are expressed as eqs 13 and 14. τij = aij +

bij

T/K Ä É bij yzÑÑÑÑ Vj ÅÅÅÅ ij zzÑÑ Λ ij = expÅÅÅ−jjjaij + z ÅÅ j T /K z{ÑÑÑÑÖ Vi ÇÅ k

In eq 3, ΔV and ΔCp signify, respectively, the difference of volume and heat capacity between the solid and liquid of the solute at fusion temperature; γ refers to the activity coefficient of the solute. Under normal pressure, the values of ΔCp and ΔV are too slight to be ignored. ΔHtp stands for the fusion enthalpy at the triple temperature Ttp. In addition, the difference between the fusion temperature Tm and triple point temperature Ttp is very small. As a result, by replacing Ttp and ΔHtp with Tm and ΔfusH, respectively, the solute solubility dependence on temperature can be simplified to eq 4. ΔfusH ijj 1 1 yz − zzz jjj R k Tm T z{

V1 ij λ 21 − λ 22 yz V i Δλ y zz = 1 expjjj− 21 zzz expjj− V2 k RT { V2 k RT {

(7)

where Vi refers to the molar volume of component i. Δλij stands for the interaction parameter (J mol−1), which relates to the interaction energy between components i and j. Nonrandom Two-Liquid (NRTL) Model. The NRTL model expressed as eqs 9−1213,15−18 was derived from the local composition concept. At present, this model is widely applied to correlate the liquid−solid phase equilibrium. ÅÄ ÑÉ N N N ∑ j = 1 τjiGjixj ∑i = 1 xiτijGij ÑÑÑÑ xjGij ÅÅÅÅ ÅÅτij − ÑÑ ln γi = +∑ N N N ÅÅ ∑i = 1 Gijxi ∑i = 1 Gijxi ÑÑÑÑ ÅÇ j = 1 ∑i = 1 Gijxi Å Ö

ΔHtp ijj 1 Ttp y 1 yzzz ΔCp jij Ttp jj − − − + 1zzzz ln(x·γ ) = ln j z j j z j z R Ttp T R k T T { k { ΔV − (p − ptp ) (3) RT

ln(x·γ ) =

V2 ij λ12 − λ11 yz V2 ij Δλ12 yz zz = expjj− zz expjj− V1 k RT { V1 k RT {

(6)

(13)

(14)

where the parameters aij and b ij are independent of composition and temperature. KAT-LSER Model. With the purpose of studying the role played by several types of solvation interaction upon solubility of a solid dissolved in neat solvents, multiple linear regression analysis (MLRA) consisting of some solvent descriptors are used. On the whole, several modes of the solvent−solute interactions are proposed. It is usual to describe a number of linear properties relating to the Gibbs energy (XYZ) of a solvent−solute solution according to the linear solvation energy relationship (LSER) via eq 15.20,21

(4)

XYZ = XYZ0 + cavity formation energy +

For a solute dissolved in a neat solvent, the activity coefficient expressed by the Wilson model13,15−18 is presented as eqs 5−8.

− solute interaction energy B

∑ solvent (15)


nitrophenylacetonitrile

C

67-56-1 64-17-5 71-23-8 67-63-0 67-64-1 78-93-3 75-05-8 141-78-6 71-36-3 78-92-2 123-91-1 108-88-3 64-19-7 110-82-7 100-41-4 7732-18-5

610-66-2

CAS Reg. No.

32.04 46.07 60.10 60.10 58.08 72.11 41.05 88.11 74.12 74.12 88.11 92.14 60.05 84.16 106.16 18.02

162.15

molar mass (g mol−1)

melting enthalpy (kJ mol−1) 14.21a

melting point (K) 351.59a 357.15b 354.65− 355.65c 354−356d Sinopharm Chemical Reagent Co., Ltd., China

786.5g 789.4g 805.3g 803.6g 789.9g 805.4g 776.8g 900.6g 809.7g 806.8g 1033.6g 871.1g 1044.6g 778.5g 870.0g 998.2 our lab

Wuhan Lullaby Pharmaceutical Chemical Co., Ltd.

source

1272e

density (295.15 K) (kg m−3)

0.995 0.997 0.995 0.995 0.997 0.996 0.995 0.996 0.995 0.996 0.997 0.995 0.996 0.996 0.995 μS cm−1

0.995

final mass fraction purity

0.995 0.997 0.995 0.995 0.997 0.996 0.995 0.996 0.995 0.996 0.997 0.995 0.996 0.996 0.995 conductivity < 2

0.982

initial mass fraction purity

none none none none none none none none none none none none none none none distillation

recrystallization

purification method

GCh GC GC GC GC GC GC GC GC GC GC GC GC GC GC conductivity meter

HPLCf

analytical method

a This work, determined at 101.2 kPa. The standard uncertainties u are u(p) = 0.43 kPa, u(T) = 0.5 K, and u(ΔfusH) = 0.43 kJ mol−1. bTaken from ref 1. cTaken from ref 23. dTaken from ref 24. eTaken from ref 27. fHigh-performance liquid phase chromatography. gTaken from ref 32. hGas chromatography.

methanol ethanol n-propanol isopropanol acetone 2-butanone acetonitrile ethyl acetate n-butanol isobutanol 1,4-dioxane toluene acetic acid cyclohexane ethylbenzene water

o-

chemicals

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

Journal of Chemical & Engineering Data Article



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method.13,25 The apparatus was provided by Tianjin Ounuo Instrument Co. Ltd., China and was validated by determining the benzoic acid solubility in pure toluene before determination.13 All determinations were made under ambient pressure (approximately 101.2 kPa). For every solubility value, triple independent determinations were carried out in parallel. An excess amount of o-nitrophenylacetonitrile was added into a 25 mL flask. After mixing violently, it was added into a thermostatic mechanical shaker at a fixed temperature. The shaking speed was set to 100 rpm. To attain the equilibration time of the studied systems, approximately 0.5 mL liquor was taken out with a 2 mL syringe at intervals of an hour and tested using the Agilent-1260 HPLC. The identical results of two analysis verified that the mixture arrived at equilibrium. In general, 11 h was adequate for all systems. At that time the flask was taken out from the shaker and allowed to precipitate the undissolved o-nitrophenylacetonitrile particles for about 2 h. The upper clear liquor was taken out cautiously, diluted, and analyzed via the Agilent-1260 HPLC. Analysis Method. The composition of the equilibrium liquor was analyzed using the Agilent-1260 HPLC, the reverse phase column used in the test had a type of LP-C18 (250 mm × 4.6 mm). The column temperature was about 303.15 K. The wavelength of the UV detector was set to 254 nm.26 Pure methanol was employed as the mobile phase and the flow rate was 0.8 mL min−1. Each analysis was repeated three times to confirm the repeatability and three samples were used for each solution at a fixed temperature. The obtained average value was regarded as the final solubility. The relative standard uncertainty for the mole fraction solubility was evaluated to be approximately 2.6%. X-Ray Powder Diffraction (XRD). So as to exhibit the existence of solvate formation or polymorph transformation of o-nitrophenylacetonitrile in experiment, the solid equilibrated with the liquid phase as well as the raw o-nitrophenylacetonitrile were tested using X-ray powder diffraction (XRD) analysis. All experiments were carried out on an instrument of Bruker AXS D8 Advance (Bruker, Germany) at a scan speed of 5° min−1. The determination of the solids was performed using Cu Kα radiation (λ = 1.54184 nm). The tube voltage was 40 kV and the tube current was 30 mA. The data was gathered from 5 to 80° (2θ) at room temperature and ambient pressure.

where XYZ0 refers to a constant. The KAT-LSER model has been extensively applied in expressing the solvent Gibbs energy for lots of reactions including the liquid−solid equilibrium using molecular characteristics of both solvent and solute according to the linear contribution of numerous solvent− solute interactions as22 2 ji V δ zy ln(x) = c0 + c1π * + c 2β + c3α + c4jjj s H zzz j 100RT z k {

(16)

In eq 16, β and α refer to, respectively, the hydrogen bond basicity and hydrogen bond acidity. π* refers to dipolarity/ polarizability of the solvent. δH represents the Hildebrand solubility parameter of the solvent, which stands for the cohesive energy density. Vs is the molar volume of the solute in a hypothetical subcooled liquid phase. The term Vsδ2H is divided by the product of universal gas constant R and T/K to make the cavity term dimensionless. In addition, with the intention of making a rational comparison among different modes, the Vs is divided by 100. c0 refers to the intercept at α = β = π* = δH = 0, c1 and c2 stand for the susceptibility of the solute properties to solute−solvent interactions of hydrogen bonding, and c3 and c4 illustrate susceptibility of the solute to nonspecific interactions.

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EXPERIMENTAL SECTION Materials. Raw o-nitrophenylacetonitrile having a purity of more than 0.982 in the mass fraction was purchased from Wuhan Lullaby Pharmaceutical Chemical Co., Ltd. Purification was performed via recrystallization in ethanol for three times. The purified o-nitrophenylacetonitrile had a mass fraction purity of 0.995, which was tested using Agilent-1260 highperformance liquid phase chromatography (HPLC). The organic solvents used here including n-propanol, methanol, toluene, ethanol, isopropanol, acetonitrile, acetone, cyclohexane, ethyl acetate, n-butanol, 2-butanone, isobutanol, acetic acid, 1,4-dioxane, and ethylbenzene were purchased from Sinopharm Chemical Reagent Co., Ltd., China. No additional purification was performed before experiment. Distilled deionized water having a conductivity of less than 2 μS cm−1 was prepared in our lab. The detailed descriptions of the above materials were tabulated in Table 1. An analytical balance purchased from the Sartorius Scientific Instrument (Beijing) was used to determine the mass of saturated solution, solute, and solvent. It had a model of CPA225D and had a standard uncertainty of 0.0001 g. Melting Properties Measurement. The fusion temperature Tm of o-nitrophenylacetonitrile may be available in the literature,1,23,24 nevertheless, its fusion enthalpy ΔfusH has not yet been reported so far. With the purpose of correlating the onitrophenylacetonitrile solubility using the thermodynamic models, a differential scanning calorimetry (DSC) instrument (Pyris-Diamond, PerkinElmer) was employed to determine the fusion enthalpy of o-nitrophenylacetonitrile under a nitrogen atmosphere. This instrument was calibrated with the reference material (indium) before experiment. Around 3 mg of onitrophenylacetonitrile was introduced into the DSC pan. The heating rate was 5 K min−1. The standard uncertainty of determination was estimated to be 0.5 K for temperature and 0.43 kJ mol−1 for ΔfusH. Solubility Determination. The determination of equilibrium solubility of o-nitrophenylacetonitrile in 16 pure solvents was carried out using the extensively employed shake-flask

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RESULTS AND DISCUSSION Melting Properties of o-Nitrophenylacetonitrile. The obtained DSC profile of o-nitrophenylacetonitrile is given in Figure 2. On the basis of DSC analysis, the fusion temperature Tm and the fusion enthalpy ΔfusH of o-nitrophenylacetonitrile are, respectively, 351.59 K and 14.21 kJ mol−1. The value of Tm measured by us is a little smaller than that reported in refs 1, 23, 24. This small difference may be due to the measured conditions, determination method, raw material purity, and so forth. According to eq 17, the fusion entropy ΔfusS for onitrophenylacetonitrile is evaluated to be 40.42 J (mol K)−1. ΔfusS =

ΔfusH Tm

(17)

XRD Analysis. The XRD patterns of the raw material onitrophenylacetonitrile and equilibrated solids with the corresponding solvents are shown graphically in Figure 3. As can be seen from the XRD patterns that all patterns of equilibrated solids with its solution present the similar D



Article

the polarity of methanol is larger than that of the other studied alcohols,27 as a result, the o-nitrophenylacetonitrile solubility is largest in methanol among these alcohols. On the other hand, the polarity of water is highest among the studied solvents; however, the o-nitrophenylacetonitrile solubility in water is lowest. Overall, it is quite difficult to illustrate the solubility behavior on the basis of a single reason. In fact, many factors may affect the solute solubility dissolved in a solvent, e.g., molecular geometry (i.e., structural and steric effect), molecule polarity, molecule size, solute−solvent, and solvent−solvent interactions. Solvent Effect on Solubility. In an attempt to understand the comprehensive features of the solvent effect, here, the KAT-LSER model is used for the solubility of o-nitrophenylacetonitrile dissolved in 16 pure solvents at 298.15 K. The needed parameters, α, β, π*, and δH are taken from the previous literature,27−31 and presented in Table 3. The molar volume of o-nitrophenylacetonitrile, Vs = 189.6 cm3 mol−1, is taken from the SciFinder database.32 The determined solubility data of o-nitrophenylacetonitrile is correlated via the solvent descriptors via multiple linear regression analysis. The regressed results are given as eq 18 for all of the selected pure solvents.

Figure 2. DSC scanning curve of o-nitrophenylacetonitrile.

characteristic peaks with the raw material o-nitrophenylacetonitrile. As a result, it may be concluded that there was no solvate formation or polymorph transformation in solubility determination. Solubility Data. The mole fraction solubilities of onitrophenylacetonitrile in n-propanol, methanol, toluene, ethanol, isopropanol, acetonitrile, acetone, cyclohexane, ethyl acetate, n-butanol, 2-butanone, isobutanol, acetic acid, water, 1,4-dioxane, and ethylbenzene at the temperatures from 278.15 to 333.15 K are presented in Table 2 and shown graphically in Figure 4. It demonstrates that the o-nitrophenylacetonitrile solubilities rise with increasing temperature for different solvents. The largest solubility value is observed in 1,4-dioxane at below 303.15 K and acetone at above 303.15 K, and lowest in water. In addition, the solubility of o-nitrophenylacetonitrile is lower in 1,4-dioxane than in acetonitrile at above 325 K. The solubility is 2940 times in 1,4-dioxane compared to that in water at 298.15 K. Figure 4 further reveals that the solubility decreases based on the sequence in different pure solvents apart from 1,4-dioxane and ethyl acetate: acetone > 2butanone > acetonitrile > toluene > (acetic acid, ethylbenzene) > methanol > ethanol > n-propanol > isopropanol > n-butanol > isobutanol > cyclohexane > water. For the systems of o-nitrophenylacetonitrile dissolved in alcohols, the sequence of o-nitrophenylacetonitrile solubility is consistent with the changing trend of the solvents’ polarity, except for isobutanol and isopropanol. It seems that the polarity of the solvent is a significant factor to influence the onitrophenylacetonitrile solubility in the alcohols. For instance,

ln(x) = −2.447(0.609) − 0.940(0.740)α − 0.675(0.993)β ij V δ 2 yz + 4.005(1.183)π * − 8.191(1.345)jjjj s H zzzz (18) k 100RT {

n = 16, R2 = 0.88, RSS = 5.61, F = 27.31

The R2 value is 0.88, which is relatively low. Therefore, we try the MLRA of ln x, except for ethylbenzene. The result is expressed as eq 19. ln(x) = −2.132(0.543) − 0.848(0.638)α − 1.243(0.892)β ij V δ 2 yz + 4.244(1.024)π * − 8.555(1.169)jjjj s H zzzz (19) k 100RT {

n = 15, R2 = 0.91, RSS = 3.77, F = 37.92

where R2 stands for the squared correlation coefficient, RSS is the residual sum of squares, and F denotes the F-test. The numbers presented in parentheses refer to the standard deviation for the equation coefficient. As is shown from eq 19 that the KAT-LSER equation comprising all solvent

Figure 3. XRD patterns of raw o-nitrophenylacetonitrile and solids in equilibration with different solvents: (a) raw material; (b) methanol; (c) ethanol; (d) n-propanol; (e) isopropanol; (f) acetonitrile; (g) acetone; (h) toluene; (i) ethyl acetate; (j) n-butanol; (k) 2-butanone; (l) isobutanol; (m) cyclohexane; (n) acetic acid; (o) water; (p) 1,4-dioxane; and (q) ethylbenzene. E



Article

Table 2. Experimental Mole Fraction Solubility (x) of o-Nitrophenylacetonitrile in 16 Pure Solvents at the Temperature Range from T = 278.15 to 333.15 K under Local Atmospheric Pressure of 101.2 kPa; x Denotes the Experimental Mole Fraction Solubility of o-Nitrophenylacetonitrile at the Studied Temperature T; RD and RAD Denote the Relative Deviation and the Average Absolute Deviation, Respectivelya 100 RD T/K

100x

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.6408 0.8417 1.052 1.307 1.741 2.350 3.051 3.953 5.139 6.606 8.423 10.85

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.4576 0.5657 0.7047 0.9394 1.180 1.557 2.128 2.766 3.827 4.871 6.492 8.376

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.4118 0.5533 0.6814 0.9172 1.155 1.506 1.957 2.541 3.334 4.261 5.436 6.851

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.4111 0.4843 0.5786 0.7510 0.9823 1.321 1.768 2.280 2.997 3.838 4.922 6.269

Apelblat equation

λh equation

Methanol 6.41 0.94 5.80 1.79 0.69 −1.79 −5.00 −5.75 −3.15 −2.15 0.32 2.71 0.13 3.53 0.04 3.81 0.61 3.78 0.35 1.56 −0.43 −3.33 0.06 −10.43 1.92 3.46 Ethanol 14.12 6.69 7.46 0.72 1.19 −4.24 1.56 −1.84 −3.91 −5.29 −4.24 −3.51 −0.79 1.67 −2.30 1.41 2.63 6.49 −0.56 2.43 1.00 0.91 −0.49 −7.16 3.36 3.53 n-Propanol 5.35 −2.68 6.46 1.16 −0.35 −3.32 1.98 1.50 −1.86 −0.17 −1.83 1.57 −1.63 2.83 −1.11 3.51 0.85 4.40 0.59 1.49 0.51 −3.83 −0.40 −14.42 1.91 3.41 Isopropanol 18.74 9.12 7.93 0.16 −2.36 −7.65 −4.26 −6.49 −4.92 −4.35 −2.24 0.55 0.32 4.57 −0.45 4.50 1.07 5.45 0.39 2.62 0.22 −2.29 −0.28 −11.84 3.60 4.97

100 RD NRTL model

Wilson model

0.20 2.28 −0.83 −4.89 −1.86 2.26 2.34 2.09 2.03 0.64 −1.87 −3.78 2.09

−0.76 2.70 −0.28 −4.54 −1.72 2.34 2.48 2.35 2.32 0.73 −2.56 −6.40 2.43

4.46 −0.11 −4.02 −1.01 −4.19 −2.52 2.29 1.60 6.24 1.90 0.51 −6.68 2.96

−0.29 1.04 −1.09 1.64 −2.44 −1.96 1.82 0.38 4.73 0.40 −0.35 −6.07 1.85

−0.93 2.76 −2.34 1.43 −1.42 −0.77 −0.29 0.20 1.84 1.03 0.13 −1.86 1.25

−0.81 2.23 −2.99 1.11 −1.21 0.05 1.05 1.80 3.21 1.44 −1.66 −8.05 2.13

−0.85 2.35 −1.11 −0.59 −1.27 0.28 1.54 −0.27 0.63 −0.26 −0.25 −0.33 0.81

−0.41 2.40 −2.74 −2.23 −1.64 1.56 4.14 2.98 3.33 0.51 −3.32 −9.98 2.94

T/K

F

100x

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 100 RAD

12.96 14.72 17.09 19.35 22.65 25.90 29.51 34.15 38.54 43.85 50.61

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

10.80 12.80 15.10 17.30 19.66 23.51 26.88 31.17 35.70 42.22 47.48 54.34

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

9.323 10.73 12.41 14.35 16.75 19.54 22.76 26.41 31.00 36.24 42.42 49.79

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

2.926 3.714 4.714 6.127 7.377 9.683 12.33 15.28 19.51 24.07 30.35 37.65

Apelblat equation

λh equation

Acetone 0.68 0.87 −0.70 −0.76 0.22 0.07 −1.28 −1.41 0.66 0.63 0.36 0.45 −0.19 0.008 0.92 1.15 −0.38 −0.21 −0.76 −0.82 0.40 −0.12 0.60 0.59 2-Butanone −0.28 −1.25 0.84 0.21 1.75 1.49 0.01 0.11 −2.35 −1.91 0.68 1.36 −0.58 0.24 −0.22 0.58 −0.88 −0.31 1.86 1.91 −0.20 −1.00 −0.33 −2.41 0.83 1.07 Acetonitrile 0.15 1.47 −0.13 0.06 −0.09 −0.57 −0.38 −1.15 0.10 −0.67 0.36 −0.19 0.26 0.06 −0.34 −0.16 0.08 0.59 −0.01 0.65 −0.09 0.42 0.05 −0.08 0.17 0.51 Toluene 1.65 1.64 0.63 0.03 −0.08 −0.91 1.88 1.11 −3.53 −4.06 0.08 −0.04 0.88 1.20 −0.74 −0.05 0.90 1.76 −0.61 0.11 0.33 0.41 −0.10 −1.39 0.95 1.06

NRTL model

Wilson model

0.27 −0.57 0.53 −1.01 0.78 0.32 −0.34 0.75 −0.47 −0.73 0.46 0.56

0.32 −0.61 0.46 −1.05 0.79 0.38 −0.27 0.80 −0.48 −0.79 0.41 0.58

−0.93 0.57 1.69 0.05 −2.25 0.82 −0.37 0.07 −0.53 2.16 −0.23 −1.34 0.92

−0.81 0.52 1.58 −0.03 −2.26 0.87 −0.29 0.15 −0.51 2.09 −0.32 −1.25 0.89

−0.03 0.02 0.13 −0.25 0.08 0.21 0.06 −0.48 0.10 0.19 0.16 −0.21 0.16

−0.84 −0.93 −0.42 −0.07 1.09 1.95 2.26 1.68 1.48 −0.19 −3.38 −8.90 1.93

−0.17 −0.09 −0.08 2.24 −3.02 0.51 1.14 −0.66 0.84 −0.71 0.24 −0.42 0.84

−0.04 −0.10 −0.20 2.09 −3.14 0.50 1.28 −0.42 1.10 −0.58 0.07 −0.92 0.87



Article

Table 2. continued 100 RD T/K

100x

288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

21.59 22.62 24.08 25.68 27.78 30.33 33.39 37.07 41.45 46.85

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

2.374 2.854 3.459 4.226 5.201 6.442 8.029 10.08 12.60 16.04 20.41

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.3321 0.4161 0.4909 0.6387 0.8029 1.024 1.301 1.714 2.281 3.033 4.044 5.460

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

12.96 14.25 15.98 17.67 19.87 21.93 24.64 27.75 31.32 35.66 40.67 46.63

278.15 283.15

0.3512 0.4366

Apelblat equation

λh equation

1,4-Dioxane −0.19 0.82 −0.11 −0.34 0.40 −0.40 0.01 −0.82 0.03 −0.45 0.02 0.10 −0.03 0.60 −0.07 0.89 −0.15 0.58 0.12 −0.30 0.11 0.53 Cyclohexane −1.87 2.51 0.14 0.77 0.07 −1.43 −0.49 −2.80 0.40 −1.59 0.39 −0.53 0.05 0.56 0.31 2.13 −0.08 2.30 −0.33 0.92 0.12 −3.14 0.39 1.70 Isobutanol −0.82 5.38 2.10 3.37 −2.41 −4.40 1.55 −2.01 0.84 −3.07 0.44 −2.71 −1.41 −3.05 −0.59 −0.26 0.34 2.52 0.37 3.74 −0.10 3.06 −0.02 0.11 0.92 2.81 Ethyl Acetate −1.15 −0.35 −0.89 −0.87 0.76 0.42 0.48 0.10 1.40 1.19 0.01 0.11 −0.01 0.41 −0.18 0.47 −0.48 0.15 −0.23 −0.02 −0.11 −0.94 0.27 −2.50 0.50 0.63 n-Butanol 12.5 2.97 4.61 −2.38

100 RD NRTL model

Wilson model

T/K

−0.05 −0.06 0.34 −0.14 −0.15 −0.09 0.01 0.16 0.10 −0.15 0.13

0.50 −0.50 −0.35 −0.57 −0.01 0.66 1.12 1.08 −0.09 −2.90 0.78

288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.5691 0.7308 0.9688 1.294 1.753 2.229 2.934 3.832 4.910 6.240

0.30 0.63 −0.35 −1.27 −0.30 0.05 0.18 0.85 0.62 0.01 −0.78 0.49

−0.41 0.96 0.14 −0.99 −0.29 −0.08 0.09 0.93 0.85 0.07 −1.84 0.61

293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

4.778 5.740 6.945 8.456 10.38 12.78 15.84 19.64 24.45

−0.65 2.12 −2.62 1.19 0.43 0.13 −1.47 −0.32 0.92 1.04 0.18 −1.14 1.02

−0.72 2.25 −2.59 1.08 0.26 0.03 −1.38 0.03 1.45 1.52 0.03 −3.13 1.21

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

2.374 2.854 3.459 4.226 5.201 6.442 8.029 10.08 12.60 16.04 20.41 26.00

0.09 −0.52 0.53 −0.11 0.69 −0.60 −0.34 −0.11 −0.0013 0.49 0.38 −0.60 0.37

0.14 −0.54 0.48 −0.14 0.69 −0.56 −0.28 −0.06 −0.01 0.40 0.26 −0.43 0.33

278.15 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 328.15 333.15 100 RAD

0.003754 0.004650 0.005571 0.006691 0.008191 0.01020 0.01250 0.01532 0.01857 0.02250 0.02742 0.03327 0.79

2.99 −1.76

−0.01 0.17

100x

Apelblat equation

λh equation

n-Butanol 1.48 −2.47 −2.61 −3.69 −2.89 −1.38 −1.78 1.70 1.29 5.89 −1.43 3.62 −0.15 3.91 0.85 2.21 0.43 −3.52 −0.34 −14.14 2.53 3.99 Acetic Acid −0.11 0.18 −0.03 −0.43 0.01 −0.45 −0.02 −0.12 0.16 0.60 0.01 0.91 −0.03 0.89 −0.08 −0.03 0.04 −2.36 0.05 0.66 Ethylbenzene −0.15 4.08 −0.06 0.90 −0.03 −1.21 0.01 −2.29 0.06 −2.49 0.07 −2.02 0.08 −1.06 0.29 0.34 −0.52 0.70 0.08 2.10 0.12 2.20 −0.04 0.71 0.12 1.67 Water 1.57 −4.21 2.44 −0.55 0.11 −0.36 −1.92 −0.08 −1.91 1.78 −0.07 4.79 0.27 5.58 0.73 5.45 0.21 2.95 −0.24 −1.61 0.02 −8.82 −0.03 −22.26 4.87 0.81

NRTL model

Wilson model

−1.78 −3.31 −1.56 0.90 4.58 1.97 2.44 1.72 −1.61 −7.03 2.64

−0.26 −2.46 −1.18 1.01 4.58 1.90 2.27 1.27 −2.75 −9.72 2.30

0.17 −0.16 −0.22 −0.14 0.25 0.29 0.27 −0.07 −0.66 0.25

1.85 −0.14 −1.24 −1.61 −1.10 −0.43 0.60 1.60 2.32 1.21

−0.10 0.10 0.08 0.02 −0.05 −0.10 −0.07 0.22 −0.44 0.29 0.34 −0.32 0.18

−0.19 0.25 0.19 −0.01 −0.18 −0.25 −0.16 0.27 −0.25 0.53 0.43 −0.72 0.29

0.10 1.54 −0.33 −1.96 −1.65 0.39 0.83 1.28 0.65 −0.03 −0.15 −0.74 2.63

−1.47 0.59 −0.53 −1.32 −0.20 2.45 3.22 3.54 2.10 −0.50 −4.25 −11.43

a

Standard uncertainties u are u(T) = 0.02 K and u(p) = 0.42 kPa and relative standard uncertainty ur is ur(x) = 0.026.

G



Article

Figure 4. Mole fraction solubility (x) of o-nitrophenylacetonitrile in the selected solvents at evaluated temperatures: ■, acetonitrile; ●, acetone; ▲, toluene; ▼, ethyl acetate; ⧫, 2-butanone; ◀, acetic acid; ▶, 1,4-dioxane; ★, ethylbenzene; □, methanol; ○, ethanol; △, n-propanol; ▽, isopropanol; ◊, n-butanol; ◁, isobutanol; ▷, cyclohexane; ☆, water; and −, calculated values via the modified Apelblat equation.

model, and nonrandom two-liquid model. The used objective function is given as eq 20.

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

α

β

π*

Vsδ2H (100RT)

methanol ethanol isopropanol n-propanol n-butanol isobutanol acetonitrile water acetone toluene ethyl acetate 2-butanone cyclohexane acetic acid 1,4-dioxane ethylbenzene

0.98 0.86 0.76 0.84 0.84 0.79 0.19 1.17 0.08 0 0 0.06 0 1.12 0 0

0.66 0.75 0.84 0.90 0.84 0.84 0.40 0.47 0.43 0.11 0.45 0.48 0 0.45 0.37 0.12

0.60 0.54 0.48 0.52 0.47 0.40 0.75 1.09 0.71 0.54 0.55 0.67 0 0.64 0.55 0.53

0.451 0.361 0.286 0.311 0.277 0.264 0.306 1.175 0.204 0.171 0.170 0.187 0.145 0.234 0.216 0.164

F=

∑ (ln γie − ln γic)2 i=1

(20)

where γei is the activity coefficient obtained using eq 4 and γci is the activity coefficient computed via solubility models. Moreover, the relative deviation (RD), root-mean-square deviation (RMSD), and relative average deviation (RAD) are also used here to assess the selected models, which are described as eqs 21, 22, and 23, respectively. xe − xc xe ÄÅ N É ÅÅ ∑ (x c − x e)2 ÑÑÑ1/2 ÅÅ i = 1 i ÑÑ i ÑÑ RMSD = ÅÅÅ ÑÑ ÅÅ N ÑÑÖ ÅÇ RD =

RAD =

a

Taken from refs 27−31.

1 N

N

∑ i=1

xie − xic xie

(21)

(22)

(23)

where N refers to the number of data points, xci and xei refer to the evaluated and experimental solubility values of o-nitrophenylacetonitrile, respectively. Throughout the regression procedure, the values of Tm and ΔfusH of o-nitrophenylacetonitrile are taken from the present work. The solvent densities presented in Table 1 are taken from ref 27. The regressed values of the model parameters, as well as the values of RMSD, are presented in Table 4. On the basis of the regressed values of the model parameters, the onitrophenylacetonitrile solubility in the 16 neat solvents is calculated at different temperatures. The acquired values of RAD and RD are also given in Table 2. Furthermore, the computed solubility data through the Apelblat equation are graphically shown in Figure 4. As is indicated from Tables 2 and 4 that the computed solubilities of o-nitrophenylacetonitrile in the 16 neat solvents coincide well with the experimental values. The maximum RMSD value is 49.66 × 10−4, which is obtained through the λh equation for 2-butanone. In addition, the RAD values are all no greater than 4.97%. One can draw a conclusion that the four models may all be suitable in correlating the solubility of onitrophenylacetonitrile in the 16 neat solvents at temperatures ranging from 278.15 to 333.15 K under 101.2 kPa. In general, the RAD values obtained using the Apelblat equation are lower than those of the other models.

properties can provide a satisfying characterization for the onitrophenylacetonitrile solubility dissolved in the 16 neat solvents with the exception of ethylbenzene. The magnitudes of model coefficients demonstrate that the relative contributions to o-nitrophenylacetonitrile solubility are, respectively, 8.29, 28.50, 5.70, and 57.46% for hydrogen bond basicity, Hildebrand solubility parameter, hydrogen bond acidity, and dipolarity/polarizability. As a result, the Hildebrand solubility parameter plays an important role in the o-nitrophenylacetonitrile solubility. The contribution of the cavity term to solubility is nearly 2 times that of the nonspecific dipolarity/polarizability term. Specific interactions interpreted through α and β of the solvent is of less contribution to the solubility of onitrophenylacetonitrile. The coefficient of the parameter π* shows positive, indicating that the o-nitrophenylacetonitrile solubility increases with an increase in dipolarity/polarizability of the solvent. In contrast, the o-nitrophenylacetonitrile solubility decreases with the increase in the hydrogen bond acidity, cohesive energy, and hydrogen bond basicity of the solvents. Solubility Correlation and Calculation. The solubility of o-nitrophenylacetonitrile dissolved in different solvents is correlated using the λh equation, Apelblat equation, Wilson H



Article

Table 4. Parameters of the Thermodynamic Equations/Models and RMSD Values for o-Nitrophenylacetonitrile in Different Solvents modified apelblat equation solvent

A

B

methanol ethanol n-propanol isopropanol acetone acetonitrile toluene 2-butanone ethyl acetate 1,4-dioxane n-butanol acetic acid isobutanol ethylbenzene cyclohexane water

−125.26 −172.81 −94.684 −102.26 −78.421 −156.56 −107.66 −57.100 −189.62 −306.50 −70.884 −320.22 −453.70 −318.37 −456.46 −132.21

1350.3 3242.3 −18.355 226.95 1343.9 4608.6 1079.9 201.89 6698.3 12 627.8 −1308.3 11 307.2 16 324.3 10 855.3 16 179.0 2417.44 λh equation

Wilson model

C

104 RMSD

a12

b12

a21

b21

104 RMSD

20.48 27.65 15.85 17.01 12.71 24.45 17.81 9.621 29.05 46.11 12.40 49.05 69.17 48.97 69.34 20.13

3.46 5.32 2.60 3.37 18.70 4.37 11.99 30.38 12.50 4.44 2.51 0.85 0.93 2.25 0.06 0.01

−5.9344 −6.2254 −4.2061 −4.8639 −3.8649 1.6231 −6.7887 −3.1918 −0.5026 6.5629 −4.7202 −3.6503 −5.1837 −5.3579 −2.7898 3.1746

2186.8 2500.8 1975.8 2221.2 998.25 29.561 2337.0 890.51 125.12 −1415.5 2243.1 1243.3 2542.5 2104.9 2495.5 833.59

44.99 39.24 19.57 66.51 10.15 13.25 10.68 7.420 8.730 11.49 127.2 50.00 12.93 11.94 20.29 5 806 461 NRTL model

−11422.8 −10195.4 193.69 −17851 −2356.4 3530.5 −2544.9 −1568.0 −1996.7 3311.4 −34508.4 1.0000 −3288.0 −3073.0 −5229.6 1.0000

21.74 15.71 16.60 19.14 18.51 13.72 15.46 36.69 10.19 4.737 18.30 23.30 5.25 6.58 0.35 0.12

solvent

λ

h

104 RMSD

a12

b12

a21

b21

α

104 RMSD

methanol ethanol n-propanol isopropanol acetone acetonitrile toluene 2-butanone ethyl acetate 1,4-dioxane n-butanol acetic acid isobutanol ethylbenzene cyclohexane water

0.1171 0.08979 0.06982 0.06208 0.5155 0.3902 0.5224 0.5215 0.1220 −0.1185 0.06857 0.1761 0.04405 0.2221 0.005298 0.0001732

33 679.2 45 801.0 54 524.7 61 461.1 3883.4 5394.2 7454.8 4233.2 6513.2 7693.0 59 175.7 15 097.5 81 815.2 14 117.6 739 518 13 005 272

34.78 19.37 29.68 22.83 19.71 12.53 20.95 49.66 36.65 18.26 26.58 20.55 5.45 18.70 0.65 0.23

11.400 −10.158 14.948 69.284 7.9468 7.7155 7.3201 6.5082 9.4708 15.005 8.9111 9.8351 9.5759 12.117 −13.332 −7.4014

−2750.6 4119.1 −3487.5 −18113.7 −2006.0 −1975.5 −1777.9 −1548.9 −2295.2 −4088.3 −2116.0 −2359.5 −2964.4 −3239.1 4615.7 2209.2

−6.4884 −5.1034 −7.1930 −0.0673 −3.6884 −3.3960 −6.0700 −3.1617 −3.2559 −4.8551 −6.2475 −1.7205 −14.490 −10.287 1.5006 9.8593

2641.9 2074.2 2827.1 515.56 1156.3 1203.6 2217.8 1034.1 906.41 1402.1 2773.7 984.96 5670.9 3474.0 1001.9 −398.67

0.36 0.20 0.26 0.20 0.46 0.47 0.45 0.47 0.21 0.20 0.39 0.47 0.21 0.20 0.20 0.20

13.72 18.02 4.39 1.35 17.98 5.88 12.51 38.02 12.60 4.61 13.47 5.85 2.25 3.84 0.17 0.01

■

■

CONCLUSIONS

AUTHOR INFORMATION

Corresponding Authors

In the present paper, the solubility of o-nitrophenylacetonitrile in 16 pure solvents was obtained experimentally at the temperatures from 278.15 to 333.15 K under ambient pressure of 101.2 kPa. The mole fraction solubility of o-nitrophenylacetonitrile increased with the increase in temperature. It obeyed the following sequence with the exception of ethyl acetate and 1,4-dioxane: acetone > 2-butanone > acetonitrile > toluene > (acetic acid, ethylbenzene) > methanol > ethanol > n-propanol > isopropanol > n-butanol > isobutanol > cyclohexane > water. KAT-LSER analysis indicated that the Hildebrand solubility parameter and polarizability/dipolarity interactions of the solvents had significant contribution to the o-nitrophenylacetonitrile solubility. The experimental solubility was correlated via the Apelblat equation, NRTL model λh equation, and Wilson model. The maximum RMSD and RAD values were, respectively, 49.66 × 10−4 and 4.97 × 10−2. The values of RAD obtained via the Apelblat equation were smaller than that of the other models.

*E-mail: [email protected]. Tel: + 86 514 87975244 (H.Z.). *E-mail: [email protected]. Tel: + 86 371 65790528 (X.L.). ORCID

Ali Farajtabar: 0000-0002-5510-3782 Hongkun Zhao: 0000-0001-5972-8352 Xinbao Li: 0000-0001-9598-3027 Notes

The authors declare no competing financial interest.

■

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o-Nitrophenylacetonitrile Solubility in Several Pure Solvents

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