Solubility Measurement and Modeling of 4,4â²-Dihydroxydiphenyl

Article pubs.acs.org/jced

Solubility Measurement and Modeling of 4,4′-Dihydroxydiphenyl Sulfone in Nine Organic Solvents from T = (278.15 to 313.15) K and Thermodynamic Property of Dissolution Yong Xie,* Hong-yan Wang, Qi-qi Jiang, and Rui Zhang School of Chemistry & Chemical Engineering, Suzhou University, Suzhou, Anhui 234000, People’s Republic of China

ABSTRACT: The solubility of 4,4′-dihydroxydiphenyl sulfone in acetonitrile, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, 1-butanol, 2-methyl-1-propanol and ethyl acetate were determined at temperatures from (278.15 to 313.15) K under 101.3 kPa by using a gravimetric method. With the increase in temperature, the solubility of 4,4′-dihydroxydiphenyl sulfone in these solvents increased. The solubility values decreased according to the following order: acetone > acetonitrile > ethyl acetate >1-butanol > (methanol, ethanol, n-propanol, 2-methyl-1-propanol) > isopropyl alcohol. The obtained solubility data were correlated with three models, which corresponded to the modified Apelblat equation, λh equation, and Van’t Hoff equation. The evaluated solubility values by the modified Apelblat equation agreed very well with those calculated by the other two models. In general, the regressed results with the three models were all within the acceptable limit for the solubility of 4,4′dihydroxydiphenyl sulfone in the selected solvents. Furthermore, the standard dissolution enthalpies per 1 mol of mixtures of 4,4′-dihydroxydiphenyl sulfone and solvent were evaluated in terms of the modified Apelblat equation. The dissolution process of 4,4′-dihydroxydiphenyl sulfone in these solvents was endothermic. The study concerning the solubility of 4,4′-dihydroxydiphenyl sulfone in the selected solvents and thermodynamic property of dissolution could provide fundamental data in the manufacturing and separating process of 4,4′-dihydroxydiphenyl sulfone.

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INTRODUCTION 4,4′-Dihydroxydiphenyl sulfone (also named Bisphenol S, CAS Reg. No. 80-09-1) with the formula (HOC6H4)2SO2 is commonly used as a plasticizing agent.1 Because of its estrogen-mimicking properties, it is widely used to replace the hazardous bisphenol A.2 4,4′-Dihydroxydiphenyl sulfone can now be found in a variety of common consumer products,3,4 and it is used as an anticorrosive agent in epoxy glues.5,6 Furthermore, it also has the advantage of being more stable to heat and light than bisphenol A.7 As a result, the production of 4,4′-dihydroxydiphenyl sulfone increases year by year. The industrial process for the preparation of 4,4′dihydroxydiphenyl sulfone requires the reaction of two equivalents of phenol with one equivalent of sulfuric acid or oleum which is subjected to a dehydration reaction. This process, however, produces a large amount of 2,4′-dihydroxydiphenyl sulfone as an isomeric byproduct together with 4,4′dihydroxydiphenyl sulfone in the electrophilic aromatic substitution reactions.8−12 The crude 4,4′-dihydroxydiphenyl sulfone contains isomer which restricts its usage in many aspects. The boiling points of the two isomers are relative high and extreme difficulty is encountered in separating the 4,4′© 2015 American Chemical Society

dihydroxydiphenyl sulfone with high purity from the resulting reaction mixture by distillation. It is well-known that the crystallization process is a critical step during the purification process of a compound. It can be employed to optimize the basic design of the crystallization procedure and improve the purity and yield of the solid. Thermodynamic parameters, especially solubility, play a critical role during the separation process and determination of the proper solvent. Therefore, the solubility data of 4,4′dihydroxydiphenyl sulfone in different solvents are especially necessary in industry. Many solvent crystallization methods have been put forward to separate the dihydroxydiphenyl sulfone isomers.13−20 Nevertheless, in previous works, the solubility data of 4,4′-dihydroxydiphenyl sulfone are very scarce. Only the solubility in esters (iso-Pr2 O, Bu2O, (C6H13)2O and MeOPh)18 and water20 are determined at one temperature. To understand the solvent crystallization process of 4,4′-dihydroxydiphenyl sulfone and obtain the Received: August 23, 2015 Accepted: November 23, 2015 Published: December 2, 2015 556

DOI: 10.1021/acs.jced.5b00714 J. Chem. Eng. Data 2016, 61, 556−564

Journal of Chemical & Engineering Data

Article

Table 1. Source and Properties of the Materials Used

chemicals 4,4′-dihydroxydiphenyl sulfone acetonitrile methanol ethanol trichloromethane isopropyl alcohol acetone toluene ethyl acetate 1-butanol a

molar mass

melting point

g·mol−1

K

source

250.27

522.65a

Nantong Baisheng Chemical Co., Ltd.

41.05 32.04 46.07 119.38 60.06 58.05 92.14 88.11 74.12

purification procedure

Sinopharm Chemical Reagent Co., Ltd., China

recrystallization in acetone

mass fraction purity

method for purity determination

0.993

HPLCb

0.996 0.995 0.997 0.994 0.997 0.995 0.996 0.996 0.995

GCc GCc GCc GCc GCc GCc GCc GCc GCc

Taken from ref 1. bHPLC normalization method. cGC normalization method.

circulated between the outer and inner walls of the flask. The temperature of the water bath was controlled by means of the thermostat. The real temperature was displayed using a thermometer (standard uncertainty: 0.02 K) inserted in the vessel. The solution was continuously stirred by using a magnetic stirrer for 24 h. A condenser was attached to the Erlenmeyer flask in order to prevent the solvent from evaporating. The equilibrium time of the system was determined by analyzing repetitively the composition of liquid phase, which was obtained with a 0.2 μm pore syringe filter every 1 h. The solution was assumed to be in equilibrium if the two analysis results were the same. The process indicated that 15 h was enough for the solution to reach equilibrium. Once the system arrived at equilibrium, the magnetic stirrer was stopped to allow any solid phase to settle from the solution. After 30 min, about 1 mL (standard uncertainty: 0.01 mL) of the upper clear solution was extracted out with a 5 mL syringe with an attached filter (PTFE 0.2 μm), which was preheated to the same temperature as the thermostatic water bath. Then the sample was transferred rapidly into a preweighed 25 mL volumetric flask. The volumetric flask was covered using a stopper and weighed with an analytical balance. Before it was tested, the solution was diluted to 25 mL with the corresponding solvent, and 1 μL of the solution was taken out to analyze by means of HPLC. During the analysis process, if the concentration of solute in the equilibrium liquid phase was low, the sample was not diluted and instead analyzed directly. Each experiment was repeated three times to check the repeatability, and three samples were taken for each solution. The average value was considered as the final solubility data point. Analysis Method. The concentration of 4,4′-dihydroxydiphenyl sulfone was tested by a Waters high-performance liquid chromatography (HPLC), which comprised a Waters 717 plus autosampler, a Waters 1525 pump, and a Waters 2487 UV detector. The detective wavelength of the UV detector was 254 nm. The injection volume of the sample was 10 μL. Pure methanol was used as a mobile phase with a flow rate of 1 mL· min−1 throughout the running time. The HPLC system was equipped with a Waters C18 reverse phase column (250 mm × 4.6 mm), the temperature of which was 303 K.

product 4,4′-dihydroxydiphenyl sulfone with high purity and yield, knowledge of the solubility of 4,4′-dihydroxydiphenyl sulfone in different solvents at various temperatures and the thermodynamic properties of solution must be known in advance. The current work has three aims: (1) determine the solubility of 4,4′-dihydroxydiphenyl sulfone in acetonitrile, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, 1butanol, 2-methyl-1-propanol, and ethyl acetate at temperatures ranging from (278.15 to 313.15) K by using a gravimetric method, (2) correlate solubility data with the Apelblat equation, λh equation, and Van’t Hoff model, and (3) calculate the dissolution property for 4,4′-dihydroxydiphenyl sulfone in different solvents.

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EXPERIMENTAL SECTION Materials. 4,4′-Dihydroxydiphenyl sulfone with a mass fraction of 0.985 was provided by Nantong Baisheng Chemical Co., Ltd., China. Purification of 4,4′-dihydroxydiphenyl sulfone was made by recrystallization in acetone for three times. The obtained 4,4′-dihydroxydiphenyl sulfone was dried in vacuum until the mass did not vary and then preserved in a desiccator. The final content of 4,4′-dihydroxydiphenyl sulfone applied in the solubility determination was 0.993 in mass fraction, which was additionally checked by using a high-performance liquid chromatography (HPLC) analysis. The solvents, including acetonitrile, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, 1-butanol, 2-methyl-1-propanol, and ethyl acetate were analytical grade. The mass fraction purity of these solvents, analyzed by gas chromatography (FULI 9790, China), were all higher than 99.4%, and used in experiment without additional purification. The properties and sources of the chemicals used in the experiment were presented in Table 1. Solubility Measurement. During the experimental process, the solubility of 4,4′-dihydroxydiphenyl sulfone in various solvents were determined by means of the gravimetric method.21−23 The temperature was controlled by using a smart thermostatic water bath with a model of DZKW-4 and a standard uncertainty of 0.02 K. The quantities of the solvent, solute, and saturated liquid were determined by means of an analytical balance with a standard uncertainty of 0.0001 g. An excessive amount of 4,4′-dihydroxydiphenyl sulfone was added to an Erlenmeyer flask filled with about 30 mL of solvent. The flask was kept at a constant temperature by water 557



Article

Table 2. Experimental Mole Fraction Solubility (x) of 4,4′-Dihydroxydiphenyl Sulfone in Different Solvents at Temperatures Ranging from T = (278.15 To 313.15) K under 101.3 kPa.a 100 RDb T/K

100 x

Van’t Hoff equation

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RADc

0.3163 0.3529 0.3910 0.4342 0.4892 0.5648 0.6548 0.7394 0.8195 0.9107 1.010 1.121 1.259 1.395 1.528

2.39 0.67 −1.71 −3.7 −3.94 −1.37 1.66 2.17 1.11 0.60 −0.06 −0.43 0.55 0.36 −0.83 1.44

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.01789 0.02081 0.02446 0.02927 0.03421 0.04028 0.04698 0.05557 0.06480 0.07540 0.08707 0.09898 0.1124 0.1255 0.1411

−5.57 −6.68 −6.43 −3.96 −3.68 −2.39 −1.81 0.42 1.46 2.51 3.02 2.24 1.21 −0.99 −1.94 2.95

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.02134 0.02543 0.02909 0.03369 0.03887 0.04502 0.05305 0.06147 0.07146 0.08148 0.09241 0.1045 0.1177 0.1295 0.1420

−7.09 −4.21 −5.32 −4.92 −4.63 −3.69 −0.78 0.63 2.54 2.77 2.68 2.05 2.40 −0.72 −3.04 3.17

278.15 280.65 283.15 285.65 288.15 290.65

0.01826 0.02114 0.02539 0.03060 0.03616 0.04258

−2.89 −5.84 −4.65 −2.80 −2.68 −2.63

modified Apelblat equation

λh equation

4.42 2.15 −0.71 −3.12 −3.72 −1.44 1.39 1.77 0.64 0.13 −0.48 −0.72 0.45 0.49 −0.39 1.47

3.10 1.28 −1.19 −3.27 −3.6 −1.13 1.81 2.25 1.13 0.56 −0.15 −0.56 0.39 0.18 −1.02 1.44

6.96 2.89 0.36 0.32 −1.4 −1.74 −2.41 −1.03 −0.48 0.41 1.10 0.78 0.52 −0.61 −0.17 1.20

−0.14 −1.80 −2.15 −0.35 −0.64 0.07 0.09 1.76 2.28 2.81 2.84 1.57 0.05 −2.67 −4.13 1.56

6.31 5.55 1.57 −0.64 −2.54 −3.37 −1.78 −1.26 0.19 0.30 0.46 0.41 1.70 −0.17 −0.86 1.81

−1.68 0.47 −1.18 −1.37 −1.65 −1.29 1.02 1.88 3.27 3.00 2.42 1.29 1.17 −2.49 −5.35 1.97

6.85 1.78 0.78 0.74 −0.68 −1.88

1.18 −2.11 −1.40 −0.04 −0.34 −0.71

Acetonitrile

Methanol

Ethanol

n-Propanol

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Table 2. continued 100 RDb T/K

100 x



λh equation

−2.69 −0.95 0.36 0.31 0.53 −0.11 0.97 −0.14 −0.35 1.28

−0.95 1.05 2.37 2.11 1.88 0.57 0.74 −1.51 −3.08 1.34

3.37 6.91 3.76 0.03 −2.51 −2.78 −1.14 −1.00 −0.53 0.91 −0.26 1.04 0.01 −0.06 −0.18 1.63

−2.30 3.18 1.41 −1.12 −2.66 −2.14 0.04 0.49 1.04 2.36 0.90 1.69 −0.02 −0.97 −2.16 1.50

2.62 0.77 0.71 −0.59 −2.07 −2.21 −0.51 0.52 0.59 0.57 0.69 0.21 −0.10 −0.33 −0.11 0.84

−1.92 −1.91 −0.37 −0.41 −0.91 −0.36 1.70 2.84 2.79 2.40 1.91 0.60 −0.78 −2.33 −3.63 1.66

3.23 3.74 2.59 0.33 −1.23 −2.66 −1.60 −1.01 −0.50 −0.80 0.70 0.64 1.41

1.62 2.46 1.58 −0.45 −1.78 −3.02 −1.78 −1.05 −0.42 −0.63 0.94 0.92 1.71

n-Propanol 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.05007 0.06003 0.07131 0.08315 0.09671 0.1114 0.1288 0.1458 0.1663

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.00912 0.01188 0.01431 0.01707 0.02049 0.02501 0.03094 0.03750 0.04536 0.05512 0.06492 0.07801 0.09113 0.1069 0.1252

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

1.026 1.134 1.270 1.398 1.529 1.687 1.887 2.088 2.279 2.475 2.681 2.876 3.079 3.287 3.513

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15

0.02269 0.02694 0.03134 0.03595 0.04141 0.04763 0.05597 0.06530 0.07592 0.08732 0.1019 0.1173 0.1350

−2.45 −0.03 1.69 1.80 1.94 1.00 1.52 −0.35 −1.56 2.25 Isopropyl Alcohol −6.08 −0.01 −1.45 −3.67 −4.87 −3.96 −1.39 −0.58 0.32 1.97 0.83 1.92 0.52 −0.11 −0.99 1.91 Acetone −4.70 −4.30 −2.37 −2.05 −2.22 −1.35 1.04 2.47 2.69 2.56 2.32 1.25 0.10 −1.22 −2.31 2.20 1-Butanol 2.35 3.09 2.13 0.03 −1.39 −2.70 −1.56 −0.91 −0.36 −0.64 0.84 0.75 1.46

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Table 2. continued 100 RDb T/K

100 x



λh equation

−0.01 −0.72 1.41

0.28 −0.44 1.27

4.96 4.69 1.94 0.80 −1.81 −2.35 0.25 −0.42 −0.83 −0.83 −0.19 0.911 0.59 0.24 −0.46 1.42

−0.46 0.99 −0.39 −0.32 −1.95 −1.73 1.37 1.01 0.71 0.60 0.94 1.54 0.55 −0.64 −2.38 1.04

6.04 3.16 −0.05 −2.16 −1.01 −2.25 −1.94 −1.92 −0.67 1.16 1.22 1.46 0.59 −0.58 −0.55 1.65

−0.46 0.99 −0.39 −0.32 −1.95 −1.73 1.37 1.01 0.71 0.6 0.94 1.54 0.55 −0.64 −2.38 1.04

1-Butanol 310.65 313.15 RAD

0.1522 0.1723

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.01156 0.01442 0.01743 0.02130 0.02550 0.03099 0.03864 0.04638 0.05554 0.06643 0.07958 0.09531 0.1125 0.1314 0.1516

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15 RAD

0.5390 0.5985 0.6603 0.7352 0.8427 0.9416 1.066 1.200 1.364 1.556 1.740 1.945 2.145 2.354 2.609

−0.04 −0.84 1.27 2-Methyl-1-propanol −4.03 −2.14 −3.19 −2.74 −4.05 −3.47 0.03 −0.01 0.01 0.22 0.87 1.77 1.08 0.19 −1.26 1.67 Ethyl Acetate 4.73 2.19 −0.71 −2.55 −1.16 −2.21 −1.77 −1.65 −0.36 1.46 1.48 1.65 0.66 −0.67 −0.83 1.61

Standard uncertainty u is u(T) = 0.02 K, and relative standard uncertainties ur are ur (p) = 0.05, ur (x) = 0.02. bRD = (xe − xc)/xe. cRAD = (1/ N)Σ(|xci − xei |)/xei . a

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RESULTS AND DISCUSSION Solubility Data. Table 2 presents the measured solubility with mole fraction of 4,4′-dihydroxydiphenyl sulfone in acetonitrile, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, 1-butanol, 2-methyl-1-propanol, and ethyl acetate within the temperature range from (278.15 to 313.15) K. Furthermore, the dependence of mole fraction solubility x upon temperature is graphically displayed in Figures 1 and 2, and the van’t Hoff plots of ln(x) versus 1/T are plotted in Figure 3. It can be seen that, with increasing temperature, the solubility of 4,4′-dihydroxydiphenyl sulfone in different solvents increases. At the same temperature, 4,4′-dihydroxydiphenyl sulfone has the largest solubility in acetone. The stronger positive dependency on temperature is found for the solvents of acetonitrile, acetone, and ethyl acetate. The mole fraction solubility data of 4,4′-dihydroxydiphenyl sulfone in the studied solvents decreases based on the following order: acetone > acetonitrile > ethyl acetate >1-butanol > (methanol, ethanol, n-

Figure 1. Solubility (x) of 4,4′-dihydroxydiphenyl sulfone with mole fraction in various solvents at different temperatures: ●, acetone; ▲, ethyl acetate; ■, acetonitrile; , calculated values from modified Apelblat equation.

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solvents are correlated by three thermodynamic models, which are Van’t Hoff equation, modified Apelblat equation, and λh equation. Van’t Hoff equation. The van’t Hoff equation describes the relationship between the natural logarithm of the solubility in mole fraction and the reciprocal of the absolute temperature.24 The van’t Hoff equation is expressed as eq 2, which is used to correlate the solubility of 4,4′-dihydroxydiphenyl sulfone in the selected solvents.

ln x = a +

b T /K

(1)

where x is the solubility in mole fraction at temperature T/K and a and b are equation parameters. On the basis of the solubility data of 4,4′-dihydroxydiphenyl sulfone in solvents, the two parameters in eq 1 can be obtained using a nonlinear regression method. Table 3 presents the regressed values of a and b together with the root-mean-square deviation (RMSD), which is defined as

Figure 2. Solubility (x) of 4,4′-dihydroxydiphenyl sulfone with mole fraction in various solvents at different temperatures: ⧫, 1-butanol; ▲, n-propanol; ●, ethanol; ■, methanol; ▼, 2-methyl-1-propanol; ☆, isopropyl alcohol; , calculated values from modified Apelblat equation.

⎡ ∑n (x e − x c)2 ⎤1/2 i i ⎥ RMSD = ⎢ i = 1 ⎢⎣ ⎥⎦ n

(2)

The relative average deviation (RAD) and relative deviation (RD) between the experimental and the evaluated solubility are described as eqs 3 and 4, respectively. RAD =

RD =

1 N

N

∑ i=1

xie − xic xie

(3)

xe − xc xe

(4)

Here N denotes the number of experimental points for a certain solvent; xci and xei denote the calculated and experimental solubility values of 4,4′-dihydroxydiphenyl sulfone at a given temperature, respectively. The calculated values of RAD and RD according to the regressed parameters’ values given in Table 3 are presented in Table 2. It indicates that all the values of RMSD are small, the largest one is 4.64 × 10−4 for the system of 4,4′-dihydroxydiphenyl sulfone + acetone. The calculated RD values are slightly larger for all studied solvents at a temperature of 273.15 K, nevertheless, the values of RD are less than 5%. On the whole, the solubility calculated via the Van’t Hoff model agrees well with the experimental values. Modified Apelblat equation. The relationship between the solubility of 4,4′-dihydroxydiphenyl sulfone in the selected nine

Figure 3. Van’t Hoff plots of ln(x) versus 1/T in different solvents: ▲, acetone; ★, ethyl acetate; ■, acetonitrile; ○, 1-butanol; △, ethanol; ▼, n-propanol; ●, methanol; ☆, 2-methyl-1-propanol; ⧫, isopropyl alcohol.

propanol, 2-methyl-1-propanol) > isopropyl alcohol. For the systems of 4,4′-dihydroxydiphenyl sulfone + n-propanol and 4,4′-dihydroxydiphenyl sulfone + ethanol, when the temperature is above 298 K, the mole fraction solubility of 4,4′dihydroxydiphenyl sulfone in n-propanol are larger than those in ethanol, and below 298 K, the case is reversed. Solubility Modeling. In the present work, the obtained solubility data of 4,4′-dihydroxydiphenyl sulfone in different

Table 3. Parameters of the Equations for 4,4′-Dihydroxydiphenyl Sulfone in Different Solvents Van’t Hoff model

a

λh equation

modified Apelblat equation

solvent

a

b

104 RMSDa

A

B

C

104RMSD

λ

h

104RMSD

acetonitrile methanol ethanol n-propanol isopropyl alcohol acetone 1-butanol 2-methyl-1-propanol ethyl acetate

8.609 9.583 8.229 11.05 13.74 6.272 9.994 13.79 9.346

−4002.66 −5050.50 −4620.95 −5461.05 −6391.51 −3005.45 −5120.32 −6345.26 −4065.83

1.01 0.16 0.20 0.13 0.08 4.64 0.09 0.089 1.94

70.98 327.78 364.08 249.18 214.09 256.44 32.83 208.60 49.72

−6789.04 −19316.01 −20554.51 −16149.66 −15409.35 −14146.87 −6144.03 −15113.00 −5870.02

−9.306 −47.45 −53.07 −35.50 −29.85 −37.34 −3.40 −29.03 −6.02

0.94 0.068 0.099 0.068 0.046 1.72 0.09 0.052 1.89

2.786 1.210 0.7063 2.247 5.400 2.073 1.182 6.172 5.130

1452.11 4341.63 6801.81 2492.54 1206.14 1514.16 4308.03 1047.14 799.22

1.01 0.20 0.25 0.30 0.094 5.09 0.095 0.11 1.92

RMSD = (Σi N= 1(xci − xei )2/N)1/2. 561



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Table 4. Predicated Values of ΔHod (kJ·mol−1) for 4,4′-Dihydroxydiphenyl Sulfone in Different Solvents T/K

acetonitrile

methanol

ethanol

n-propanol

isopropyl alcohol

acetone

1-butanol

2-methyl-1-propanol

ethyl acetate

278.15 280.65 283.15 285.65 288.15 290.65 293.15 295.65 298.15 300.65 303.15 305.65 308.15 310.65 313.15

34.92 34.73 34.54 34.34 34.15 33.96 33.76 33.57 33.38 33.18 32.99 32.80 32.60 32.41 32.22

50.87 49.89 48.90 47.91 46.93 45.94 44.96 43.97 42.98 42.00 41.01 40.02 39.04 38.05 37.07

48.16 47.05 45.95 44.85 43.75 42.64 41.54 40.44 39.33 38.23 37.13 36.02 34.92 33.82 32.71

52.17 51.44 50.70 49.96 49.22 48.49 47.75 47.01 46.27 45.53 44.80 44.06 43.32 42.58 41.84

59.08 58.45 57.83 57.21 56.59 55.97 55.35 54.73 54.11 53.49 52.87 52.25 51.63 51.01 50.39

31.26 30.48 29.70 28.93 28.15 27.38 26.60 25.82 25.05 24.27 23.49 22.72 21.94 21.17 20.39

43.21 43.14 43.07 43.00 42.93 42.85 42.78 42.71 42.64 42.57 42.5 42.43 42.36 42.29 42.22

58.52 57.91 57.31 56.71 56.10 55.50 54.90 54.29 53.69 53.09 52.48 51.88 51.28 50.67 50.07

34.87 34.75 34.62 34.50 34.37 34.25 34.12 34.00 33.87 33.75 33.62 33.50 33.37 33.25 33.12

equation. However, they are no more than 5.1 × 10−4. All the RAD values evaluated by the λh equation are all less than 2.0%. The values of RMSD and RAD obtained by using the λh equation are nearly the same with those obtained with the modified Apelblat equation. The conclusion can be drawn from Tables 2 and 3 that the experimental solubility of 4,4′dihydroxydiphenyl sulfone in the nine solvents at different temperatures under 101.3 kPa show good agreement with the calculated ones attained using the three models. The correlation results with Apelblat equation are better than those acquired with the λh equation and Van’t Hoff model except for the 4,4′-dihydroxydiphenyl sulfone + acetone system. In the Buchowski−Ksiazaczak λh equation, the parameter λ relates the mean value of association amount of solute molecules in solution. Table 3 further reveals that the values of λ are all small in the selected solvents, no obvious association come into being during the dissolution process of 4,4′dihydroxydiphenyl sulfone. The h is in relation to the molar dissolution enthalpy of a solute. Thermodynamic Properties for the Dissolution. Calculation for thermodynamic properties of dissolution of a solid in solvents will provide a better way to understand the theoretical features of solution structure. From the energetic point of view, the dissolution of a solid in a solvent depends upon the change of thermodynamic property. Provided that the water activity coefficient at normal temperature equals to 1, according to the Gibbs−Helmholtz equation, the molar dissolution enthalpy can be derived and expressed as eq 7:29,30

solvents and the absolute temperature T can be fitted via the modified Apelblat equation,25,26 which is described as ln x = A +

B + C ln T T

(5)

In eq 5, A and B are model constants, the values of which reveal the influence of mixture nonideality upon the solubility of a solute and the variation of solute activity coefficient, respectively. The value of model parameter C stands for the influence of temperature on the fusion enthalpy of a solute. The values of the three parameters A, B, and C, along with the values of RMSD are obtained by using the nonlinear regression method based on the measured solubility and presented in Table 3. The calculated solubility of 4,4′-dihydroxydiphenyl sulfone in different solvents based on the regressed parameters are plotted in Figures 1 and 2, and the obtained values of RAD and the RD are listed in Table 2. From Tables 2 and 3, we can see that the values of RMSD are no more than 1.89 × 10−4, and the RAD is 1.65 × 10−4, which are smaller values than those obtained with the Van’t Hoff model. The solubility values evaluated by means of the modified Apelblat equation agree well with the experimental results. So the experimental solubility of 4,4′-dihydroxydiphenyl sulfone in these organic solvents at various temperatures can be correlated by using the modified Apelblat equation. λh equation. The Buchowski−Ksiazaczak λh equation is an alternative method to characterize the solution behavior. It is put forward first by Buchowski et al.27,28 and experessed as eq 6. It only comprises two parameters λ and h. The Buchowski− Ksiazaczak λh equation could be used to correlate the experimental solubility for many systems. In the present work, the solubility data of 4,4′-dihydroxydiphenyl sulfone are also correlated with the Buchowski−Ksiazaczak λh equation. ⎛1 ⎡⎛ λ(1 − x c) ⎞⎤ 1 ⎞ ln⎢⎜1 + ⎟⎥ = λ h ⎜ − ⎟ c ⎠⎦ x Tm ⎠ ⎣⎝ ⎝T

⎡ ∂ ln x ⎤ ΔHdo = RT ⎢ = R( −B + CT ) ⎣ ∂ ln T ⎥⎦

(7)

The calculated values of ΔHod at solubility data points are presented in Table 4. It shows that the molar enthalpy (ΔHod) for the dissolution process of 4,4′-dihydroxydiphenyl sulfone are all positive. The positive values of ΔHod demonstrate that the dissolution process of 4,4′-dihydroxydiphenyl sulfone is endothermic in the studied solvents. The endothermic behavior possibly results from more powerful interactions between 4,4′dihydroxydiphenyl sulfone and 4,4′-dihydroxydiphenyl sulfone molecules. The newly formed bond energy is too weak between the 4,4′-dihydroxydiphenyl sulfone molecule and the solvent molecule; it cannot make up for the energy needed for destroying the primary bond, and subsequently the system requires absorbing extra heat from circumstance. The positive

(6)

where Tm is the melting temperature of 4,4′-dihydroxydiphenyl sulfone, which is 522.65 K.1 The two parameters, λ and h, are acquired by regressing the experimental solubility data with eq 6 and are also presented in Table 3. It demonstrates that the calculated RMSD values obtainedwith the λh equation are a little larger than those obtained with the modified Apelblat 562



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Hoff model, modified Apelblat equation, and λh equation. The modified Apelblat equation provides more accurate results than the Van’t Hoff and λh equations. As a whole the solubility values evaluated by means of the three models were all acceptable for the system of 4,4′-dihydroxydiphenyl sulfone in the studied solvents. The dissolution enthalpies per mole of mixture were derived according to the modified Apelblat equation parameters. The results indicated that the dissolution process of 4,4′-dihydroxydiphenyl sulfone in these solvents was endothermic.

values of molar dissolution enthalpy also show repulsive interaction between the molecules of solvent and 4,4′dihydroxydiphenyl sulfone. Figure 4 presents the relationship between the dissolution enthalpy of 4,4′-dihydroxydiphenyl sulfone and temperature in

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AUTHOR INFORMATION

Corresponding Author

*Tel: + 86 557 2871736. Fax: + 86 557 2871736. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS

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REFERENCES

This work is financial supported by the Natural Science Foundation of the Anhui Province (Project number: 1408085MB40).

(1) Li, J. X.; Chan, C. M. Fluidity and Heat Resistance of Polyphenylene Oxide Compounded with Crystalline Plasticizer. Polym. Bull. 2011, 66, 831−840. (2) Chen, M. Y.; Ike, M.; Fujita, M. Acute Toxicity, Mutagenicity, and Estrogenicity of Bisphenol-A and Other Bisphenols. Environ. Toxicol. 2002, 17, 80−86. (3) Liao, C.; Liu, F.; Kannan, K. Bisphenol S, a New Bisphenol Analogue, in Paper Products and Currency Bills and its Association with Bisphenol A Residues. Environ. Sci. Technol. 2012, 46, 6515− 6522. (4) Liao, C.; Liu, F.; Guo, Y.; Moon, H. B.; Nakata, H.; Wu, Q.; Kannan, K. Occurrence of Eight Bisphenol Analogues in Indoor Dust from the United States and Several Asian Countries: Implications for Human Exposure. Environ. Sci. Technol. 2012, 46, 9138−9145. (5) Viñas, P.; Campillo, N.; Martínez-Castillo, N.; HernandezCordoba, M. Comparison of Two Derivatization-Based Methods for ́ Solid-Phase Microextraction-Gas Chromatography-Mass Spectrometric Determination of Bisphenol A, Bisphenol S And Biphenol Migrated From Food Cans. Anal. Bioanal. Chem. 2010, 397, 115−125. (6) Changkhamchom, S.; Sirivat, A. Synthesis and Properties of Sulfonated Poly(ether ketone ether sulfone) (S-PEKES) via Bisphenol S: Effect of Sulfonation. Polym. Bull. 2010, 65, 265−281. (7) Kuruto-Niwa, R.; Nozawa, R.; Miyakoshi, T.; Shiozawa, T.; Terao, Y. Estrogenic Activity of Alkylphenols, Bisphenol S, and their Chlorinated Derivatives using a GFP Expression System. Environ. Toxicol. Pharmacol. 2005, 19, 121−130. (8) Andreas, B. E.; Gunter, C. Process for Making 4,4′Dihydroxydiphenyl Sulfone. US Patent 4,996,367, Feb 26, 1991. (9) Ogata, E.; Nate, N. Process for Preparation of 4,4′Dihydroxydiphenylsulfone. US Patent 5,189,223, Feb 23, 1993. (10) Ogata, E.; Nate, N. Process for Producing High-purity 4,4′Dihydroxydiphenyl Sulfone. US Patent 7,456,321, Nov 25, 2008. (11) Akzo, N. V. Preparation of 4,4′-Dihydroxydiphenyl Sulfone. EP Patent 0,293,037, Nov 30, 1988. (12) Ma, H. H.; Zhang, S. J.; Shi, J. M. Recent Research Progress on Preparation of Bisphenol S. Chem. Ind. Prog. 2001, 20, 22−25 (Chinese). (13) Ogata, E.; Ono, K.; Nakagaki, S. 4,4′-Dihydroxydiphenylsulphone Preparation of High Purity from Phenol and Sulphuric Acid in Presence of Solvents. DE Patent 2,708,388, Aug 31, 1978.

Figure 4. Enthalpy of dissolution of 4,4′-dihydroxydiphenyl sulfone in nine organic solvents at different temperatures: (a) ■, acetonitrile; ●, methanol; ▲, ethanol; ▼, n-propanol; ⧫, isopropyl alcohol; (b) ◀, acetone; ▶, n-butanol; ○, 2-methyl-1-propanol; △, ethyl acetate.

the selected solvents. The linear dependence of the dissolution enthalpy upon the temperature is found for a certain solvent. This behavior demonstrates that the dissolution heat capacity remains at a constant during the dissolution procedure of 4,4′dihydroxydiphenyl sulfone in the studied solvents. It can also be seen from Figure 4 that the dissolution enthalpy of 4,4′dihydroxydiphenyl sulfone shows a positive dependence on temperature for the solvents of acetonitrile, n-butanol, and ethyl acetate, and for the other solvents, the case is reversed.

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CONCLUSION The solubility data of 4,4′-dihydroxydiphenyl sulfone in nine pure organic solvents were determined experimentally at the temperatures between 278.15 and 313.15 K under 101.3 kPa by means of the gravimetric method. The solubility data of 4,4′dihydroxydiphenyl sulfone in the studied pure solvents increased with increasing temperature; however, the increments with temperature were different for different solvents. At a given temperature, the solubility values ranked as acetone > acetonitrile > ethyl acetate >1-butanol > (methanol, ethanol, npropanol, 2-methyl-1-propanol) > isopropyl alcohol. The obtained solubility data were fitted successfully with the Van’t 563



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