Solubility Determination and Modeling of Sodium

Dec 30, 2015 - College of Chemical Engineering, Ningbo University of Technology, Ningbo, ... Chinese Academy of Sciences, Ningbo Institute of Material...
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Solubility Determination and Modeling of Sodium Mononitrobenzenesulfonate in Different Solvents at Temperatures Ranging from 283.15 to 323.15 K Guoquan Zhou,† Yan Zhang,‡ Yujing You,§ Hao Chen,‡ Qizhong Zhou,‡ Aiguo Zhong,*,‡ and Rongrong Li*,‡ †

College of Chemical Engineering, Ningbo University of Technology, Ningbo, Zhejiang 315016, P. R. China School of Pharmaceutical and Chemical Engineering, TaiZhou University, Linhai, Zhejiang 317000, P. R. China § Chinese Academy of Sciences, Ningbo Institute of Material Technology & Engineering, Ningbo, Zhejiang, 315211, P. R China ‡

ABSTRACT: The equilibrium solubilities of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran were measured experimentally by using a steady-state method at temperatures ranging from 283.15 to 323.15 K under 101.3 kPa. The solubilities of sodium 3-nitrobenzenesulfonate increased faster in ethanol than in the other solvents as the temperature increase. The order of the solubility values from high to low was: ethanol > acetone > tetrahydrofuran > 1-butanol > ethyl acetate > cyclohexanone. For the systems of sodium 4nitrobenzenesulfonate + solvents, the sequence of the mole fraction solubility data was: acetone > ethanol > (cyclohexanone, 1butanol) > (ethyl acetate, tetrahydrofuran). The experimental solubility data were correlated with the modified Apelblat equation and λh equation. The results indicated that the calculated values via the modified Apelblat equation agreed well with experimental results for sodium 3/4-nitrobenzenesulfonate.

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INTRODUCTION Sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate are all important intermediate materials. Sodium 3nitrobenzenesulfonate is widely used for the synthesis of advanced pigments, dyes, and polymers,1−4 and sodium 4nitrobenzenesulfonate, in nucleophilic substitution reaction,5 controlling of the mode of polymorphic transition,6 and effect of ionic liquids on a class of charge-neutral nucleophiles.7 Generally, the isomeric mixture of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate with various proportions is obtained simultaneously by sulfonation of nitrobenzene with concentrated sulfuric acid or sulfur trioxide.8−10 The crude sodium mononitrobenzenesulfonate mixture restricts its usage in many aspects. In order to obtain pure sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate, the isomeric mixture must be separated. Some methods via solvent crystallization have been put forward to separate the isomeric mixture of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate.11−13 Crystallization process is the critical step that determines the quality of the final product. The solubilities of solid compounds in solvents play an important role in the development and © 2015 American Chemical Society

operation of crystallization process. Therefore, knowing the solubility of the two substances is necessary. The solubilities of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in some solvents are reported in literature. To the best of the authors’ present knowledge, Li and co-workers determined the solubilities of sodium 3nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in binary solvent mixtures of NaCl + H2O, Na2SO4 + H2O, and C2H5OH + H2O at different temperatures14,15 and the ternary sodium 3-nitrobenzenesulfonate + sodium 4-nitrobenzenesulfonate + water system.16 In order to enrich the solubility data and provide the comprehensive basic data for engineering application, the aims of the present work are to (1) determine experimentally the solubility of 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran at different temperatures and (2) correlate the solubility data by using the modified Apelblat equation and λh equation. Received: September 13, 2015 Accepted: December 22, 2015 Published: December 30, 2015 636

DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

Journal of Chemical & Engineering Data

Article

Table 1. Source and Purity of the Materials Used chemicals

molar mass (g·mol−1)

melting point (K)

sodium 3nitrobenzenesulfonate sodium 4nitrobenzenesulfonate ethanol ethyl acetate acetone 1-butanol cylohexanone tetrahydrofuran

225.15

623.25a

225.15

384.43b

a

melting enthalpy (kJ·mol−1)

source

8.32

Shanghai Reagent Factory YuanCheng Chemical Co. Ltd. Shanghai Chemical Reagent Co.

46.07 88.11 58.05 74.12 98.14 72.11

purification method

mass fraction purity

analytical method

0.995

HPLCc

0.995

HPLCc

>0.998 >0.998 >0.998 >0.998 >0.998 >0.998

GCd GC GC GC GC GC

Taken from ref 14. bThis work. Standard uncertainties u are u(T) = 0.5 K and u(ΔfusH) = 400 J·mol−1. cHigh-performance liquid chromatography. Gas chromatography.

d

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three measurements was considered as the final value of the analysis. The relative standard uncertainty of the measurement was estimated to be 0.02. DSC Measurement. The melting temperature of sodium 3nitrobenzenesulfonate was determined in the literature;14 however, it was not found for sodium 4-nitrobenzenesulfonate. In this work, the melting point Tm of sodium 4-nitrobenzenesulfonate was measured by a differential scanning calorimetry (type: NETZSCH 204 F1). The experiment was carried out under nitrogen atmosphere with a flow rate of 5 mL·min−1. The temperature and heat flow for the instrument were precalibrated with indium as the reference material. The mass of sample was about 1.5 mg, and the heating rate was 5 K· min−1. The standard uncertainties were estimated to be 0.5 K for the temperature and 400 J·mol−1 for the melting enthalpy.

EXPERIMENTAL SECTION Materials. Sodium 3-nitrobenzenesulfonate and sodium 4nitrobenzenesulfonate were provided by Shanghai Reagent Factory (China) and YuanCheng Chemical Co. Ltd. (China), respectively. They all had a purity of 0.995 in a mass fraction and were used without further purification. The solvents, including ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran (purchased from Shanghai Chemical Reagent Co. of China) were of analytical grade, and their mass fraction purities were all higher than 0.998. The detailed information on these substances was presented in Table 1. Apparatus and Procedure. The steady-state method was used to measure the solubility of sodium 3/4-nitrobenzenesulfonate in diffeent solvents in the present work. The detailed information on solubility determination was similar to that used in the literatures.17−19 An analytical balance with a standard uncertainty of 0.0001 g was employed to determine the mass of the saturated solution. Excessive amount of sodium 3-nitrobenzenesulfonate or sodium 4-nitrobenzenesulfonate was added into a 125 mL Erlenmeyer flask filled with 50 mL of organic solvent. The flask was placed into a constant-temperature bath. The solution was stirred using a Teflon-coated magnetic stirring bar. The water temperature was controlled by a constant-temperature water bath (Neslab, model RTE-101; standard uncertainty, 0.01 K). A condenser was connected to the flask to prevent the solvent from evaporating. Excess solute was placed in the flask and allowed to equilibrate in a constant temperature water bath at a given temperature for at least 3 days. Attainment of equilibrium was verified both by repetitive measurements after a minimum of 3 additional days and by approaching equilibrium from supersaturation by preequilibrating the solutions at a higher temperature. Thirty minutes prior to sampling, stirring was ceased to allow any solid phase to settle down from the solution. The upper clear liquid was taken out with a 5 mL preheated syringe attached with a filter (PTFE 0.2 μm) and then analyzed with a high-performance liquid chromatography. Analysis. Aliquots of saturated sodium 3/4-nitrobenzenesulfonate solution were transferred into a tarred volumetric flask through a coarse filter. The concentrations of sodium 3/4nitrobenzenesulfonate in different solvents were determined using an Agilent 1200 high-performance liquid phase chromatograph (HPLC). The Diamonsil C18 (150 mm × 4.6 mm) chromatographic column was used. The mobile phase consisted of three eluents which were water, Na2SO4, and H3PO4. Each analysis was repeated three times, and the average value of the

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RESULTS AND DISCUSSION Property of Pure Component. Figure 1 is the determined DSC curve of sodium 4-nitrobenzenesulfonate. According to

Figure 1. DCS scan of sodium 4-nitrobenzenesulfonate.

the DSC analysis, the melting temperature Tm (mean extrapolated onset temperature) and melting enthalpy ΔfusH of sodium 4-nitrobenzenesulfonate are 384.43 K and 8.32 kJ· mol−1, respectively. The melting entropy ΔfusS for sodium 4-nitrobenzenesulfonate was evaluated to be 21.64 J·(mol·K)−1 by using eq 1.

ΔfusS =

ΔfusH Tm

(1)

Solubility Data. The solubilities of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in 637

DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

Journal of Chemical & Engineering Data

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Table 2. Mole Fraction Solubility of Sodium 3/4-Nitrobenzenesulfonate (x) in Different Solvents under 101.3 kPaa sodium 3-nitrobenzenesulfonate

sodium 4-nitrobenzenesulfonate

c

1000 xc

1000 x T/K 283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

e

1000 x 2.811 3.61 4.539 5.813 6.991 8.663 10.45 12.75 15.31

Apelblat equation 2.847 3.619 4.557 5.687 7.038 8.640 10.53 12.73 15.30

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.03945 0.04579 0.05374 0.06223 0.07268 0.08650 0.1033 0.1175 0.1352

0.03860 0.04564 0.05381 0.06325 0.07412 0.08661 0.1009 0.1173 0.1360

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.7887 0.8687 0.9654 1.081 1.201 1.370 1.540 1.747 1.940

0.7812 0.8690 0.9694 1.084 1.215 1.364 1.535 1.730 1.952

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.5514 0.5626 0.5863 0.6152 0.6396 0.6595 0.6878 0.7161 0.7449

0.5354 0.5590 0.5835 0.6089 0.6352 0.6623 0.6904 0.7195 0.7495

283.15 288.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15

0.02130 0.02193 0.02265 0.02371 0.02488 0.02609 0.02754 0.02917 0.03212

0.0214 0.02192 0.02264 0.02356 0.0247 0.02608 0.0277 0.02959 0.03179

283.15 288.15 293.15 298.15 303.15 308.15 313.15

0.6173 0.6289 0.6546 0.6941 0.7455 0.8030 0.8699

0.6128 0.6322 0.6598 0.6962 0.742 0.7983 0.8664

λh equation Ethanol 2.896 3.629 4.523 5.610 6.928 8.526 10.47 12.82 15.70 Ethyl Acetate 0.03916 0.04594 0.05379 0.0629 0.07349 0.08584 0.1003 0.1174 0.1378 Acetone 0.7804 0.8705 0.9716 1.086 1.215 1.362 1.531 1.727 1.956 1-Butanol 0.5451 0.5672 0.5900 0.6135 0.6378 0.6628 0.6887 0.7154 0.7431 Cyclohexanone 0.0205 0.02164 0.02282 0.02405 0.02533 0.02665 0.02802 0.02945 0.03093 Tetrahydrofuran 0.5736 0.6190 0.6667 0.7168 0.7694 0.8246 0.8825 638

1000 x

Apelblat equation

λh equation

1.037 1.183 1.328 1.467 1.641 1.805 2.045 2.317 2.596

1.057 1.175 1.309 1.461 1.634 1.830 2.053 2.307 2.594

1.055 1.174 1.309 1.46 1.631 1.826 2.050 2.310 2.613

0.08838 0.09957 0.1092 0.1199 0.1311 0.1428 0.1569 0.1748 0.1930

0.09002 0.09866 0.1083 0.1189 0.1307 0.1438 0.1584 0.1745 0.1924

0.0904 0.09869 0.1079 0.1182 0.1299 0.1430 0.1581 0.1754 0.1956

e

12.05 14.00 16.13 18.20 20.60 22.87 25.77 28.97 32.25

12.20 13.99 15.96 18.12 20.49 23.07 25.88 28.92 32.2

12.43 14.03 15.82 17.84 20.14 22.75 25.76 29.23 33.27

0.3182 0.4053 0.4979 0.5966 0.6986 0.7983 0.9473 1.106 1.312

0.3363 0.4056 0.4863 0.5800 0.6882 0.8125 0.9548 1.117 1.301

0.3376 0.4035 0.4808 0.5716 0.6783 0.8041 0.9531 1.130 1.343

0.9064 0.9125 0.9173 0.9265 0.9383 0.9543 0.9667 0.9912 1.0148

0.9079 0.9109 0.917 0.9262 0.9382 0.9530 0.9705 0.9907 1.0137

0.9063 0.9117 0.9186 0.9273 0.9381 0.9517 0.9685 0.9895 1.016

0.1088 0.1124 0.1171 0.1219 0.1266 0.1320 0.1381

0.1092 0.1126 0.1165 0.1211 0.1263 0.1323 0.1389

0.1092 0.1126 0.1166 0.1210 0.1261 0.1319 0.1387 DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

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Table 2. continued sodium 3-nitrobenzenesulfonate

sodium 4-nitrobenzenesulfonate

c

1000 xc

1000 x T/K 318.15 323.15 a

e

1000 x

0.9399 1.048

Apelblat equation 0.9482 1.046

λh equation

1000 x

Apelblat equation

λh equation

Tetrahydrofuran 0.9432 1.007

0.1454 0.1555

0.1463 0.1545

0.1466 0.1558

e

Standard uncertainties u are u(T) = 0.02 K, u(p) = 500 Pa; relative standard uncertainty ur(x) = 0.02; xe, experimental values; xc, calculated values.

ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran are presented in Table 2. The dependence of solubilities of sodium 3/4-nitrobenzenesulfonate in different solvents on temperature was plotted in Figures 2−4.

Figure 4. Solubility x of sodium 3/4-nitrobenzenesulfonate at different temperatures: ■, sodium 4-nitrobenzenesulfonate in acetone; ●, sodium 3-nitrobenzenesulfonate in ethanol; , calculated values with the modified Apelblat equation.

acetone are greater than those in other five solvents. The sequence of the mole fraction solubility data in these solvents from high to low is acetone > ethanol > (cyclohexanone, 1butanol) > (ethyl acetate, tetrahydrofuran). When the temperature is below 313 K, the solubilities of sodium 4-nitrobenzenesulfonate are higher in cyclohexanone than in 1butanol, nevertheless, it is vice versa when the temperature is above 313 K. The similar behavior can also be found for the systems of sodium 4-nitrobenzenesulfonate + ethyl acetate and sodium 4-nitrobenzenesulfonate + tetrahydrofuran. Table 2 also further shows that, for a certain solvent, the solubility of sodium 3-nitrobenzenesulfonate are smaller than those of sodium 4-nitrobenzenesulfonate in the solvents of ethyl acetate and cyclohexanone; and in ethanol, the case is vice versa. While in the solvent of acetone, the solubility of sodium 3-nitrobenzenesulfonate equals approximately to those of sodium 4-nitrobenzenesulfonate. In order to illustrate the difference of solubility behavior of sodium 3/4-nitrobenzenesulfonate in the studied solvents, some properties of these solvents, e.g. polarities, dipole moments (μ), dielectric constants (ε), and Hildebrand solubility parameters (δH) are showed in Table 3.20 Table 3

Figure 2. Solubility x of sodium 3-nitrobenzenesulfonate in different solvents: ●, ethyl acetate; ▲, acetone; ▼, 1-butanol; ⧫, cyclohexanone; ◀, tetrahydrofuran; , calculated values with the modified Apelblat equation.

Figure 3. Solubility x of sodium 4-nitrobenzenesulfonate in different solvents: ■, ethanol; ▲, 1-butanol; ▼, ethyl acetate; ⧫, cyclohexanone; ◀, tetrahydrofuran; , calculated values with the modified Apelblat equation.

It can be seen from Table 2 and Figures 2−4 that the solubilities of sodium 3/4-nitrobenzenesulfonate in ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran are functions of temperature, and they all increase with an increase in temperature. The solubilities of sodium 3nitrobenzenesulfonate in selected solvents decrease according to the following order: ethanol > acetone > tetrahydrofuran > 1-butanol > ethyl acetate > cyclohexanone. For the systems of sodium 3-nitrobenzenesulfonate + solvents, the solubilities of sodium 3-nitrobenzenesulfonate show a stronger dependency on temperature in ethanol than in the other solvents. For the systems of sodium 4-nitrobenzenesulfonate + solvents, the solubility of sodium 4-nitrobenzenesulfonate in

Table 3. Physical Properties for the Selected Solvents: ε Denotes Dielectric Constants; μ Denotes Dipole Moments; δH Denotes Hildebrand Solubility Parametersa

a

639

solvent

polarity

μ

ε (293.15 K)

δH

ethanol ethyl acetate acetone 1-butanol cyclohexanone tetrahydrofuran

65.4 23 35.5 60.2 28 21

1.7 1.7 2.9 1.66 3.1 1.75

22.4 6.02 20.6 18.2 18.2 7.6

13.4 9.1 10.0 11.4 9.9 9.1

Taken from ref 20. DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

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and Figure 2 show that, for the solvents of alcohol, the order of the sodium 3-nitrobenzenesulfonate solubility from high to low is in accord with the four properties of the solvents. However, for the other solvents, they rank as the dipole moment, dielectric constants (ε) and Hildebrand solubility parameters (δH) except for cyclohexanone. The polarity and dielectric constants of solvents are key factors to affect the solubility of sodium 3-nitrobenzenesulfonate. For sodium 4-nitrobenzenesulfonate, the order of solubility values from high to low is in accord with the dielectric constants (ε) and Hildebrand solubility except for acetone, and with dipole moments (μ) and polarity except for acetone and n-butanol. In general, it is very complicated to explain the phenomenon shown in Figures 2−4 according to a single reason. The case may due to many factors, for example, the rule of “like dissolves like,” the hydrogen bond, van der Waals force and polarity, and so on. The main reason is still unclear and needs further investigation. Solubility Correlation. In this work, the solubility values of sodium 3/4-nitrobenzenesulfonate in the selected organic solvents were correlated by modified Apelblat equation21−23 and λh equation.24,25 Modified Apelblat Equation. The modified Apelblat equation was used extensively in the solubility correlation.21−23 In this work, it is employed to correlate the solubility data of sodium 3/4-nitrobenzenesulfonate in the studied solvents. The modified Apelblat equation is expressed as eq 2. B ln x = A + + C ln T T

Figure 6. Van’t Hoff plots of ln(x) versus 1/T in different solvents for sodium 4-nitrobenzenesulfonate: ●, ethanol; ▲, acetone; ▼, 1butanol; ⧫, ethyl acetate; ◀, cyclohexanone; ▶, tetrahydrofuran.

nitrobenzenesulfonate is determined in this work, which is 384.43 K. The solubility of sodium 3/4-nitrobenzenesulfonate in different solvents are correlated using eqs 2 and 3 by means of a nonliner regression method. The regressed values of A, B, and C in eq 2 and λ and h in eq 3, along with the root-meansquare deviations (RMSD) are given in Table 4. The rootmean-square deviations (RMSD) is defined as ⎡ ∑n (x c − x e)2 ⎤1/2 i i ⎥ RMSD = ⎢ i = 1 ⎢⎣ ⎥⎦ n

(2)

In eq 2, A, B, and C are three adjustable parameters. x represents the mole fraction solubility of sodium 3/4nitrobenzenesulfonate in solvents at absolute temperature T/K. λh Equation. The λh equation with two adjustable parameters is also widely used to correlate the solubility data.24,25 It is expressed as eq 3, which is a semiempirical equation put forward by Buchowski and co-workers.24,25 ⎡ 1 ⎛ λ(1 − x) ⎞ 1 ⎤ ln⎜1 + ⎟ = λh⎢ − ⎥ ⎝ ⎠ x Tm/K ⎦ ⎣ T /K

(4)

In addition, the relative average deviation (RAD) is also employed, which expression is described as eq 5. RAD =

1 N

N

∑ i=1

xie − xic xie

(5)

xci

In eqs 4 and 5, denotes the calculated solubility value of sodium 3/4-nitrobenzenesulfonate in solvent based on the regressed values of equation parameters, xei is the experimental solubility data, and n is the number of data points. The calculated values of relative average deviation (RAD) are also presented in Table 4, and the evaluated solubility values are presented in Table 2. Furthermore, the calculated solubilities of sodium 3/4-nitrobenzenesulfonate in the selected solvents using the modified Apelblat equation are also shown graphically in Figures 2−4. Table 4 shows that the largest RMSD value is 1.20 × 10−4 and the RAD value 1.86% for the modified Apelblat equation. Nevertheless, the acquired values of RMSD and RAD with the λh equation are a little larger than those with the modified Apelblat equation. The largest ones of RMSD and RAD are 4.36 × 10−6 and 2.82%, respectively. So the calculated solubilities with the modified Apelblat equation agree well with the experimental ones. The modified Apelblat equation can be used to correlate the solubility of sodium 3/4-nitrobenzenesulfonate in the selected solvents at different temperatures. In eq 3, the λ value reflects nonideality of a solution, which relates to the average association number of solute molecules, and the value of h stands for solution enthalpy. Table 4 further illustrates that the values of λ are very small; no obvious association is formed during the solution process of sodium 3/ 4-nitrobenzenesulfonate in solvents. The h values are all positive, which demonstrates that there exists repulsive interaction force between sodium 3/4-nitrobenzenesulfonate and the solvent.

(3)

Here Tm is the melting point of sodium 3-nitrobenzenesulfonate or sodium 4-nitrobenzenesulfonate under normal pressure, and λ and h are two model parameters. Van’t Hoff plots of ln(x) versus 1/T are shown in Figures 5 and 6. The melting point (Tm) of sodium 3-nitrobenzenesulfonate is taken from ref 14, and the melting point of sodium 4-

Figure 5. Van’t Hoff plots of ln(x) versus 1/T in different solvents for sodium 3-nitrobenzenesulfonate: ■, ethanol; ●, ethyl acetate; ▲, acetone; ▼, 1-butanol; ⧫, cyclohexanone; ◀, tetrahydrofuran. 640

DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

Journal of Chemical & Engineering Data

Article

Table 4. Parameters of the Equations for Sodium 3/4-Nitrobenzenesulfonate in Different Solventsa λh Equation

modified Apelblat equation

a

solvent

A

B

C

ethanol ethyl acetate acetone 1-butanol cyclohexanone tetrahydrofuran

35.163 −58.15 −143.35 −30.77 −215.32 −291.17

−5081.14 −262.51 4370.14 399.15 8449.31 11748.84

−4.088 8.664 21.40 3.867 30.95 42.91

ethanol ethyl acetate acetone 1-butanol cyclohexanone tetrahydrofuran

−131.84 −100.70 6.754 −12.58 −86..01 −127.56

3899.22 2653.54 −2369.12 −2395.74 3344.95 4665.76

19.698 14.525 −0.4946 2.313 11.90 18.06

100 RAD

104 RMSD

λ

Sodium 3-Nitrobenzenesulfonate 0.66 0.54 0.07567 1.04 0.01 2.842 × 0.58 0.09 1.496 × 0.20 0.014 2.990 × 0.55 0.002 4.505 × 0.55 0.045 4.050 × Sodium 4-Nitrobenzenesulfonate 0.80 0.14 1.909 × 0.77 0.01 6.585 × 0.56 1.20 0.03601 1.86 0.12 3.598 × 0.12 0.02 −8.889 × 0.43 0.01 −8.354 ×

h

10−4 10−3 10−4 10−5 10−3 10−3 10−5 10−3 10−4 10−5

100 RAD

104 RMSD

46839.33 7.983 7.687 7.585 1.339 2.673

× × × × ×

106 105 105 107 105

1.45 0.99 0.74 0.46 1.97 2.82

1.60 0.01 0.11 0.03 0.06 0.25

5.813 8.931 4.031 7.335 4.727 1.864

× × × × × ×

105 106 104 105 106 107

0.82 1.04 1.57 2.55 0.12 0.40

0.14 0.02 4.36 0.19 0.01 0.01

RMSD = [(∑Ni=1(xci − xei )2)/N]1/2; RAD = (1/N)∑Ni=1|(xei − xci )/xei |.

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(ethylenediamine)cobalt(III) 2-chloro, 5-nitrobenzenesulphonate Monohydrate. J. Mol. Struct. 2006, 800, 93−99. (2) Wang, A. G. One Kind of Dye Additive. CN Patent 104,805,713, July 29, 2015. (3) Sha, Z. Z.; Liu, Z. G.; Zhu, C.; Yan, Q. H.; Shang, A. G.; Cheng, C. Y.; Yuan, H.; Zeng, L. X. Brilliant Yellow Reactive Dye Mixture with Good Insolation, Sweat Stain and Friction Resistances and Application Thereof in Printing and Dyeing of Hydroxyl-Containing Fiber Material. CN Patent 104,804,469, July 29, 2015. (4) Gasser-Ramirez, J. L.; Harris, J. M. Quantitative Confocal Raman Microscopy Study of Ion-interaction Retention at Reversed-Phase Chromatographic Interfaces. Anal. Chem. 2010, 82, 5743−5750. (5) Ford, J. W.; Janakat, M. E.; Lu, J.; Liotta, C. L.; Eckert, C. A. Local Polarity in CO2-expanded Acetonitrile: A Nucleophilic Substitution Reaction and Solvatochromic Probes. J. Org. Chem. 2008, 73, 3364−3368. (6) Horiguchi, M.; Okuhara, S.; Shimano, E.; Fujimoto, D.; Takahashi, H.; Tsue, H.; Tamura, R. Control of the Mode of Polymorphic Transition Inducing Preferential Enrichment by Modifying the Molecular Structure or Adding Seed Crystals: Significant Influence of CH/F Hydrogen Bonds. Cryst. Growth Des. 2008, 8, 540− 548. (7) Crowhurst, L.; Lancaster, N. L.; Perez Arlandis, J. M.; Welton, T. Manipulating Solute Nucleophilicity with Room Temperature Ionic Liquids. J. Am. Chem. Soc. 2004, 126, 11549−11555. (8) Chen, J. X.; Wang, F. Preparation Process of Sodium m-Nitrobenzenesulfonate. J. Jilin Inst. Chem. Technol. 2004, 21, 9−11 (Chinese). (9) Chen, Y. Z.; Su, Y. H.; Jiao, F. J.; Chen, G. W. A Simple and Efficient Synthesis Protocol for Sulfonation of Nitrobenzene under Solvent-Free Conditions via a Microreactor. RSC Adv. 2012, 2, 5637− 5644. (10) Shen, Y. X.; Qin, S. C.; Zhang, S. Q.; Qin, Y. P. Vanadium Catalyst for Nitrobenzene Sulfonation, and its Preparation Method. CN Patent 103,752,336, Apr 30, 2014. (11) Brunnmueller, F.; Boehm, W.; Weberdoerfer, V. Separation of Water-soluble Salts of Aromatic Sulfonic Acids from Sulfonation Mixtures. DE Patent 3,020,526, Dec 10, 1981. (12) Timofeev, A. M.; Endyus’kin, P. N.; Gramina, V. F.; Zasypkina, M. P.; Smirnov, E. G. Isolation of Sodium m-Nitrobenzenesulfonate from the Reaction Mixture during its Preparation. SU Patent 1,081,161, Mar 23, 1984. (13) Cerveny, L.; Marhoul, A.; Ruzicka, V.; Hora, A. Refining of Water-soluble Nitrobenzenesulfonates. CS Patent 209,628, Dec 31, 1981. (14) Li, R. R.; Liang, H. D.; Ge, C. H.; Lin, C. P.; You, Y. J.; Zhao, B. Equilibrium Solubility of Sodium 3-Nitrobenzenesulfonate in Binary

CONCLUSION The solubilities of sodium 3-nitrobenzenesulfonate and sodium 4-nitrobenzenesulfonate in ethanol, acetone, 1-butanol, ethyl acetate, cyclohexanone, and tetrahydrofuran were determined at temperatures from 283.15 to 323.15 K. The solubilities of sodium 3-nitrobenzenesulfonate showed stronger temperature dependency in ethanol than in the other solvents. In selected solvents, they decreased with the following order: ethanol > acetone > tetrahydrofuran > 1-butanol > ethyl acetate > cyclohexanone. For the sodium 4-nitrobenzenesulfonate, the solubility were greater in acetone than in other five solvents. The sequence of the mole fraction solubility data from high to low was: acetone > ethanol > (cyclohexanone, 1-butanol) > (ethyl acetate, tetrahydrofuran). The solubility data determined in this work were correlated with the modified Apelblat equation and λh equation. The calculated solubilities with the modified Apelblat equation agreed well with the experimental values. The modified Apelblat equation could be used to correlate the solubility of sodium 3/4-nitrobenzenesulfonate in the selected solvents at different temperatures.

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AUTHOR INFORMATION

Corresponding Authors

*Tel.: +86 576 85486698. Fax: +86 576 85137169. E-mail address: [email protected]. *Tel.: +86 576 85486698. Fax: +86 576 85137169. E-mail address: [email protected]. Funding

This work is financially supported by National Natural Science Foundation of China (No. 21207095, 21506138, 21542010), Natural Science Foundation of Zhejiang Province, China (LY14B030006, LY14B020012), Natural Science Foundation of Ningbo (2013A610020), and Taizhou Science and Technology Plan Projects (1402ky15). Notes

The authors declare no competing financial interest.

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REFERENCES

(1) Sharma, R.; Sharma, R. P.; Bala, R.; Pretto, L.; Ferretti, V. Second-sphere Coordination in Non-spherical Anion Binding: Synthesis, Characterization and X-ray Structure of cis-Diazidobis641

DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642

Journal of Chemical & Engineering Data

Article

NaCl + H2O, Na2SO4 + H2O, and C2H5OH + H2O Solvent Mixtures at Elevated Temperatures from (273.15 to 323.15) K. J. Chem. Eng. Data 2012, 57, 3434−3437. (15) Li, R. R.; Lin, J.; Ying, A. G.; You, Y. J.; Li, C. H. Solubility of Sodium 4-Nitrobenzenesulfonate in Binary Sodium Chloride + Water, Sodium Sulfate + Water, and Ethanol + Water Solvent Mixtures at Elevated Temperatures. J. Chem. Eng. Data 2012, 57, 427−430. (16) Li, R. R.; Zhao, H. K.; Jiang, M.; Wang, Y.; Wang, Q. F. Solid Liquid Equilibria of the Ternary Sodium 3-Nitrobenzenesulfonate + Sodium 4-Nitrobenzenesulfonate + Water System. J. Chem. Eng. Data 2011, 56, 2955−2959. (17) Nývlt, J. Solid-Liquid Phase Equilibria; Publishing House of the Czechoslovak Academy of Sciences: Prague, 1977. (18) Li, D. Q.; Evans, D. G.; Duan, X. Solid-Liquid Equilibria of Terephthalaldehydic Acid in Different Solvents. J. Chem. Eng. Data 2002, 47, 1220−1221. (19) Zhao, H. K.; Li, R. R.; Ji, H. Z.; Zhang, D. S.; Tang, C.; Yang, Li. Q. Equilibrium Solubility of 3- and 4-Nitrophthalic Acids in Water. J. Chem. Eng. Data 2007, 52, 2072−2073. (20) Smallwood, I. M. Handbook of Organic Solvent Properties; Amold: London, 1996. (21) Li, W. X.; Yi, J. K.; Yao, G. B.; Zhao, H. K. Solubility Measurement and Correlation for 3,5-Dichloroaniline in (Methanol + Water) and (Ethanol + Water) Mixed Solvents. J. Chem. Eng. Data 2014, 59, 3831−3841. (22) Zhao, H. K.; Ji, H. Z.; Meng, X. C.; Li, R. R. Solubility of 3Chlorophthalic Anhydride and 4-Chlorophthalic Anhydride in Organic Solvents and Solubility of 3-Chlorophthalic Acid and 4-Chlorophthalic Acid in Water from (283.15 to 333.15) K. J. Chem. Eng. Data 2009, 54, 1135−1137. (23) Apelblat, A.; Manzurola, E. Solubilities of o-Acetylsalicylic, 4Aminosalicylic, 3,5-Dinitrosalicylic, And p-toluic Acid, and Magnesium-DL-aspartate in Water from T = (278 to 348) K. J. Chem. Thermodyn. 1999, 31, 85−91. (24) Buchowski, H.; Ksiazczak, A.; Pietrzyk, S. Solvent Activity along a Saturation Line and Solubility of Hydrogen-Bonding Solids. J. Phys. Chem. 1980, 84, 975−979. (25) Zhao, H. K.; Xu, H.; Yang, Z. P.; Li, R. R. Solubility of 3,4Dichloronitrobenzene in Methanol, Ethanol, and Liquid Mixtures (Methanol + Water, Ethanol + Water): Experimental Measurement and Thermodynamic Modeling. J. Chem. Eng. Data 2013, 58, 3061− 3068.

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DOI: 10.1021/acs.jced.5b00783 J. Chem. Eng. Data 2016, 61, 636−642