Measurement of SolidâLiquid Phase Equilibrium for the Ternary 3

Article pubs.acs.org/jced

Measurement of Solid−Liquid Phase Equilibrium for the Ternary 3‑Nitrophthalic Anhydride + 4‑Nitrophthalic Anhydride + 1,4Dioxane System Fangli Qiu,† Jianguo Yang,† Guobo Huang,† Huanan Hu,† Siying Yu,† Hongkun Zhao,*,§ and Rongrong Li*,†,‡ †

Institute of Applied Chemistry, TaiZhou University, Linhai, Zhejiang 317000, P. R. China Industrial Catalysis Institute of Zhejiang University of Technology, Hangzhou, Zhejiang 310014, P. R. China § College of Chemistry & Chemical Engineering, YangZhou University, YangZhou, Jiangsu 225009, P. R. China ‡

ABSTRACT: In this work, solid−liquid equilibria (SLE) data for the ternary 3nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system were obtained at (283.15, 303.15, and 323.15) K. The solid−liquid phase diagrams of the ternary system were constructed based on the measured solubility data. There existed two pure solid phases at each temperature in the studied system, pure 3-nitrophthalic anhydride and 4nitrophthalic anhydride, which were identified by the wet residue method of Schreinemaker. Furthermore, the density (ρ) of the equilibrium liquid phase was determined. The ternary phase diagram and solubility data for the system 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane, which shows a much more practical application for the region where pure 3-nitrophthalic anhydride and 4-nitrophthalic anhydride are obtained, are much larger than those in the system with 2-propanone as a solvent.

■

INTRODUCTION This is a continuation of our previous work, and the applications of 3-nitrophthalic anhydride (CAS Registry No. 641-70-3) and 4-nitrophthalic anhydride (CAS Registry No. 5466-84-2) have already been previously described.1 The structural formulas of 3- and 4-nitrophthalic anhydride are displayed in Figure 1.

high purity of 3- and 4-nitrophthalic anhydride is difficult. In the present work, the concern is regarding the systematic determination of the solubility of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride in 1,4-dioxane. The optimum seeking method is closely related to the solubility of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride in 1,4-dioxane. The solid−liquid phase equilibrium diagram of the 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system is critical to obtain the high purity of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride. It is also very important to study the system and ensure an optimal separation process. Solid−liquid phase equilibrium data are of the upmost importance when dealing with crystallization processes. The solid−liquid phase diagram of the ternary 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system has not been previously reported on to the best of our present knowledge. The solubility of the ternary 4-nitro-2-benzofuran1,3-dione + 5-nitro-2-benzofuran-1,3-dione + 2-propanone system has already been reported in the previous publications;1 however it remains a challenge to get the pure 3-nitrophthalic anhydride at low temperature if the mixture of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride was in the region of high concentration of 4-nitrophthalic anhydride. The region where pure 3-nitrophthalic anhydride and 4-nitrophthalic anhydride are obtained is much larger than that in the system

Figure 1. Structural formulas of 3-nitrophthalic anhydride and 4nitrophthalic anhydride.

3-Nitrophthalic anhydride and 4-nitrophthalic anhydride are generally produced by dehydrating from the nitrophthalic acid, which are produced by the nitration of phthalic anhydride using concentrated sulfuric acid.2−8 This method creates isomeric mixtures of 3- and 4-nitrophthalic anhydride. The products of 3- and 4-nitrophthalic anhydride are usually obtained via crystallization from the isomeric mixture. However, obtaining a © 2014 American Chemical Society

Received: January 8, 2014 Accepted: March 25, 2014 Published: April 2, 2014 1583

dx.doi.org/10.1021/je500171d | J. Chem. Eng. Data 2014, 59, 1583−1587

Journal of Chemical & Engineering Data

Article

system. Each measurement was repeated three times, and the average data of three measurements was considered as the final data of the analysis (precision, ± 0.1 %).1

of 2-propanone solvent, and it is much more convenient in practical application. Therefore, the main goal of this work was to study and gain solid−liquid phase equilibrium diagrams of the 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system at (283.15, 303.15, and 323.15) K. The diagrams were obtained by using Schreinemakers’ wet residue method9−15 and allowed the influence of temperature on the ternary system to be determined.

■

RESULTS AND DISCUSSION The equilibrium solubility data and density (ρ) of the equilibrium liquid phase for the ternary 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system at (283.15, 303.15, and 323.15) K are presented in Tables 2, 3,

■

EXPERIMENTAL SECTION Materials. The 3- and 4-nitrophthalic anhydride were supplied by YuanChen Chemical Co. Ltd., and the solvent of 1,4-dioxane for experimental use was supplied by Shanghai Reagent Factory (China). All three compounds were utilized without any additional purification, and high-performance liquid chromatography (HPLC) was used to measure and determine the purity of the substances. Karl Fisher titration was used to check the quantity of water in the compounds of 3nitrophthalic anhydride and 4-nitrophthalic anhydride, which can be seen in Table 1, and there was no water in the compounds. The water used in the experiment was deionized (conductivity < 5 μS·cm−1).

Table 2. Mass Fraction Solubility of the Ternary 4Nitrophthalic Anhydride (1) + 3-Nitrophthalic Anhydride (2) + 1,4-Dioxane (3) System at T = 283.15 K and Pressure p = 0.1 MPaa liquid phase

Table 1. Purities and Suppliers of Chemicals materials 3-nitrophthalic anhydride 4-nitrophthalic anhydride 1,4-dioxane (AR)b a

mass fraction purity ⩾ 0.992 ⩾ 0.992 ⩾ 0.995

sources YuanChen Chemical Co. Ltd. (China) YuanChen Chemical Co. Ltd. (China) Shanghai Reagent Factory (China)

analytical method

quantity of watera

HPLC

none

HPLC

none

wet solid phase

density of liquid phase

100w1

100w2

100w1

100w2

(g·mL−1)

solid phase

0 2.82 6.43 9.03 11.91 14.89 16.03 17.83 19.13 20.82 23.13 25.45 27.59 29.51

33.04 31.18 29.33 27.31 26.26 25.66 22.63 18.29 14.80 11.08 7.64 4.96 2.51 0

0 1.81 4.06 4.06 5.08 30.42 49.55 71.56 57.56 67.44 55.30 58.80 54.91 73.13

64.57 62.13 52.65 63.77 69.30 43.00 13.77 6.32 7.56 4.68 4.51 2.82 1.41 0

1.0301 1.0326 1.0413 1.0467 1.0564 1.0704 1.0612 1.0470 1.0415 1.0341 1.0296 1.0260 1.0229 1.0221

M M M M M M+N N N N N N N N N

a w, mass fraction; M, 3-nitrophthalic anhydride; N, 4-nitrophthalic anhydride. Standard uncertainties u are u(T) = 0.02 K and ur(w) = 0.02, and the combined expanded uncertainty Uc is Uc(ρ) = 0.0005 g· mL−1 (0.95 level of confidence).

Analytical method: Karl Fisher titration. bAR, analytical reagent.

Apparatus and Procedure. Schreinemaker’s wet residue method was implemented in the experimental procedure, and the specific method was illustrated in detail in previous works.1 The temperatures (of solvent and of a compound investigated) in the two ebulliometers at a given pressure were measured simultaneously by two 2850D-type probes of the Hewlett− Packard quartz thermometer (model HP-2801A). Both probes were repeatedly calibrated against a Leeds & Northrup standard platinum 25Ω resistance thermometer (model 8163-B) coupled in a four-wire connection with a precision resistance bridge model F17A (Automatic Systems Laboratories, Milton Keynes, UK). When sufficient new solids had been generated in the evaporating containers, the solids were separated from the solutions. The quantity of water in our fluids was also measured by Karl Fisher titration to make sure there was no water in the equilibrium system. Analysis. Aliquots of the saturated 3-nitrophthalic anhydride and 4-nitrophthalic anhydride solution were taken at each respective temperature and removed into volumetric flasks. An Agilent 1100 HPLC was used to analyze the mass fraction of 3nitrophthalic anhydride and 4-nitrophthalic anhydride in aqueous solutions. The method used to analyze the content of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride and the densities (ρ) of the equilibrium liquid phase was the same in our previous work. We also used the method of Karl Fisher titration to measure the quantity of water in our fluids and the compounds of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride, and the results show that there was no water in the

Table 3. Mass Fraction Solubility of the Ternary 4Nitrophthalic Anhydride (1) + 3-Nitrophthalic Anhydride (2) + 1,4-Dioxane (3) System at T = 303.15 K and Pressure p = 0.1 MPaa liquid phase

wet solid phase


100w1

100w2

100w1

100w2

(g·mL−1)

solid phase

0 2.50 4.75 8.63 11.75 14.56 15.49 16.99 18.21 21.05 23.42 26.36 29.01 32.00

41.06 40.53 38.64 36.63 35.35 34.39 30.70 26.81 22.29 17.04 11.82 7.33 3.89 0

0 1.34 3.05 4.11 7.00 32.17 51.05 59.04 56.15 60.21 57.00 59.89 54.48 76.66

67.76 66.88 61.49 70.44 61.81 47.97 17.26 13.36 12.02 8.41 6.49 4.00 2.59 0

1.0531 1.0607 1.0752 1.0841 1.0975 1.1144 1.0893 1.0715 1.0624 1.0535 1.0447 1.0390 1.0322 1.0301

M M M M M M+N N N N N N N N N

a

w, mass fraction; M, 3-nitrophthalic anhydride; N, 4-nitrophthalic anhydride. Standard uncertainties u are u(T) = 0.02 K and ur(w) = 0.02, and the combined expanded uncertainty Uc is Uc(ρ) = 0.0005 g· mL−1 (0.95 level of confidence). 1584



Article

and 4, respectively. The SLE phase diagrams are also shown for the two respective temperatures in Figures 2, 3, and 4. In these Table 4. Mass Fraction Solubility of the Ternary 4Nitrophthalic Anhydride (1) + 3-Nitrophthalic Anhydride (2) + 1,4-Dioxane (3) System at T = 323.15 K and Pressure p = 0.1 MPaa liquid phase

wet solid phase


100w1

100w2

100w1

100w2

(g·mL−1)

solid phase

0 1.97 4.96 8.13 11.06 13.6 14.67 15.97 17.37 19.13 21.05 23.75 26.29 29.91 32.45 34.59

53.6 52.6 50.45 48.76 47.91 47.51 42.21 36.74 31.82 26.97 22.13 16.59 12.58 8.13 3.5 0

0 1.19 3.44 4.06 6.77 33.07 54.91 58.18 48.53 61.06 56.77 60.89 64.56 58.18 56.55 63.66

67.98 70.15 68.28 74.49 67.27 51.07 22.40 18.68 19.75 13.15 12.13 8.63 5.76 4.68 2.03 0

1.1325 1.1357 1.1407 1.1494 1.1707 1.2104 1.1699 1.1524 1.1346 1.1195 1.0993 1.0776 1.0643 1.0491 1.0435 1.0365

M M M M M M+N N N N N N N N N N N

Figure 3. Phase diagram for the ternary 3-nitrophthalic anhydride + 4nitrophthalic anhydride + 1,4-dioxane system at 303.15 K; C2, cosaturated point of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride; E2, solubility of 3-nitrophthalic anhydride in 2-propanone; S2, solubility of 4-nitrophthalic anhydride in 1,4-dioxane; w1, w2, W, N, and M have the same meaning as described in Figure 2; ■ and ● are the experimental solubility data, which are given in Table 3, in the liquid and solid phases, respectively.

a

w, mass fraction; M, 3-nitrophthalic anhydride; N, 4-nitrophthalic anhydride. Standard uncertainties u are u(T) = 0.02 K and ur(w) = 0.02, and the combined expanded uncertainty Uc is Uc(ρ) = 0.0005 g· mL−1 (0.95 level of confidence).

Figure 4. Phase diagram for the ternary 3-nitrophthalic anhydride + 4nitrophthalic anhydride + 1,4-dioxane system at 323.15 K; C3, cosaturated point of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride; E3, solubility of 3-nitrophthalic anhydride in 2-propanone; S3, solubility of 4-nitrophthalic anhydride in 1,4-dioxane; w1, w2, W, N, and M have the same meaning as described in Figure 2; ■ and ● are the experimental solubility data, which are given in Table 4, in the liquid and solid phases, respectively. Figure 2. Phase diagram for the ternary 3-nitrophthalic anhydride + 4nitrophthalic anhydride + 1,4-dioxane system at 283.15 K; w1, mass fraction of 4-nitrophthalic anhydride; w2, mass fraction of 3nitrophthalic anhydride; W, 1,4-dioxane; M, 3-nitrophthalic anhydride; N, 4-nitrophthalic anhydride; C1, cosaturated point of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride; E1, solubility of 3-nitrophthalic anhydride in 1,4-dioxane; S1, solubility of 4-nitrophthalic anhydride in 1,4-dioxane; ■ and ● are the experimental solubility data, which are given in Table 2, in the liquid and solid phases, respectively.

anhydride and 4-nitrophthalic anhydride saturated with equilibrium solution. The subscripts of 1, 2, and 3 correspond to (283.15, 303.15, and 323.15) K, respectively, for all of the aforementioned nomenclature. From Figures 2, 3, and 4, along solubility curves E1C1, E2C2, or E3C3, connecting the composition points of saturated liquid phase and corresponding wet residue and extended, the point of junction of these tie-lines is approximately the pure solidphase component for 3-nitrophthalic anhydride. The saturation curves E1C1, E2C2, and E3C3 correspond to the solid phase of 3nitrophthalic anhydride at (283.15, 303.15, and 323.15) K respectively Similarly, connecting the solubility curves S1C1, S2C2, or S3C3, linking the component points of the equilibrium liquid phase and wet solid phase and also prolonged, the point of crossing of these tie-lines is the approximate solid-phase component for 4-nitrophthalic anhydride. The saturation

diagrams, 1,4-dioxane, 3-nitrophthalic anhydride, and 4-nitrophthalic anhydride are represented by the letters W, M, and N, respectively. Moreover, points E1, E2, and E3 represent the equilibrium solubility of 3-nitrophthalic anhydride in 1,4dioxane, and S1, S2, and S3 represent the equilibrium solubility of 4-nitrophthalic anhydride in 1,4-dioxane. C1, C2, and C3 are invariant points which show the two pure solids 3-nitrophthalic 1585



Article

curves S1C1, S2C2, and S3C3 correspond to the solid phase of 4nitrophthalic anhydride. As illustrated in Figures 2, 3, and 4, the ternary phase diagrams are divided into four regions by two solubility curves. The regions in the SLE phase diagram are represented as follows: I, unsaturated region (E1WS1C1 in Figure 2, E2WS2C2 in Figure 3, and E3WS3C3 in Figure 4); II, crystalline region of solid 3-nitrophthalic anhydride (E1MC1 in Figure 2, E2MC2 in Figure 3, and E3MC3 in Figure 4); III, crystalline region of solid 4-nitrophthalic anhydride (S1NC1 in Figure 2, S2NC2 in Figure 3, and S3NC3 in Figure 4); IV, cocrystalline region of solids 3nitrophthalic anhydride and 4-nitrophthalic anhydride (NMC1 in Figure 2, NMC2 in Figure 3, and NMC3 in Figure 4). Figures 2, 3, and 4 further demonstrate the temperature influence on the equilibrium phase diagram for the ternary system of 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane. The solubility of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride increase with the increase in temperature from (283.15 to 323.15) K, and the cosaturated point moves upward. The crystalline fields of 3-nitrophthalic anhydride increase as the temperature decreases, but crystalline fields of 4-nitrophthalic anhydride increase with the temperature. The crystallization field of 4-chlorophthalic anhydride is larger than that of 3-chlorophthalic anhydride at the same temperature. The region where can gain the pure 4-nitrophthalic anhydride is much larger than that in the system of solvent of 2-propanone.1 The relationship between the concentration values of 4nitrophthalic anhydride and the density of the equilibrium liquid phase was established from data in Tables 2, 3, and 4 and is displayed in Figures 4, 5, and 6. The maximum observed in

Figure 6. Density (ρ) value−composition relationship diagram for the ternary 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4dioxane system at 303.15 K: w1, mass fraction of 4-nitrophthalic anhydride; ■, experimental data point; , experimental relationship diagram.


liquid phase was gained. There existed two pure solid phases 3nitrophthalic anhydride and 4-nitrophthalic anhydride, which were identified by the wet residue method of Schreinemakers’ at each temperature in the studied system. For each respective temperature, the SLE phase diagram has three crystallization fields, one invariant point, and two univariant curves in the ternary 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane system. The ternary phase diagram and solubility data for the system 3-nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4-dioxane, which shows a much more practical application for the region where pure 3-nitrophthalic anhydride and 4-nitrophthalic anhydride are obtained, are much larger than those in the system with 2-propanone as a solvent.


■

the density values correspond to the maximum total content of 4-nitrophthalic anhydride and 3-nitrophthalic anhydride. The inflection points which the maximum observed in the density values in Figures 5, 6, and 7 correspond to the cosaturated points C1 in Figure 2, C2 in Figure 3, and C3 in Figure 4.

AUTHOR INFORMATION

Corresponding Authors

*Tel.: +86 576 85486698. Fax: +86 576 85137169. E-mail: lrr@ tzc.edu.cn (R.L.). *Tel.: +86 514 87975568. Fax: +86 514 87975244. E-mail address: [email protected] (H.Z.).

■

CONCLUSIONS The solid−liquid equilibrium phase diagrams for the ternary 3nitrophthalic anhydride + 4-nitrophthalic anhydride + 1,4dioxane system at (283.15, 303.15, and 323.15) K were constructed experimentally, and the density (ρ) of equilibrium

Funding

This project was supported by the Natural Science Foundation of Zhejiang Province, China (LQ12B03002, LY12B02004), National Natural Science Foundation, China (21207095), Science and technology plan project of Zhejiang province 1586



Article

(2012C37028, 2011C37055), Science and technology plan project of Taizhou (102XCP08). Notes

The authors declare no competing financial interest.

■ ■

ACKNOWLEDGMENTS We appreciate the editors and the anonymous reviewers for their valuable suggestions. REFERENCES

(1) Li, R. R.; Han, D. M.; Pan, F. Y.; Jia, W. P.; Jin, Y. X.; Zhao, J.; You, Y. J. Solid−Liquid Equilibria of Ternary 4-Nitro-2-benzofuran1,3-dione + 5-Nitro-2-benzofuran-1,3-dione + 2-Propanone at 283.15 and 323.15 K. J. Chem. Eng. Data 2013, 58, 682−685. (2) Liu, Z. M. Method for Preparing 3-Nitrophthalic acid. Patent CN 1,405,143, March 26, 2003. (3) Furrer, P.; Beyeler, H. Process for separating mixtures of 3- and 4nitrophthalic acid. Patent US 4,284,797, August 18, 1981. (4) Liu, Z. M.; Lu, X. H. Preparation technology of purified 4nitrophthalic acid. Patent CN 1,651,399, August 10, 2005. (5) Littmann, E. R. Production of 3-nitrophthalic acid. Patent US 1,549,885, August 18, 1925. (6) Odle, R. R. Nitration of phthalic acid and phthalic anhydride using nitric acid. Patent US 5,155,234, October 13, 1992. (7) Littmann, E. R. The preparation of 3-nitrophthalic acid. J. Am. Chem. Soc. 1925, 47, 1980−1981. (8) Bogert, M. T.; Boroschek, L. Some experiments with the mononitroortho-phthalic acids. J. Am. Chem. Soc. 1901, 23, 740−761. (9) 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. (10) Zhao, H. K.; Li, R. R.; Ji, H. Z.; Zhang, D. S.; Tang, C.; Yang, Li. Q. Equilibrium solubility of 3- and 4-nitrophthalic acid in water. J. Chem. Eng. Data 2007, 52, 2072−2073. (11) Zhao, H. K.; Li, R. R.; Zhang, D. S.; Zhang, Q. H.; Ji, H. Z.; Yuan, Y. Solid−liquid phase equilibrium and phase diagram for ternary 3-nitrophthalic acid−4-nitrophthalic acid−water system at 283.15 and 333.15 K. Fluid Phase Equilib. 2008, 265, 25−29. (12) Stephen, H.; Stephen, T. Solubility of Inorganic and Organic Compounds; Pergamon: Oxford, 1979. (13) Nývlt, J. Solid-Liquid Phase Equilibria; Publishing House of the Czechoslovak: Prague, 1977. (14) Schott, H. A mathematical extrapolation for the method of wet residues. J. Chem. Eng. Data 1961, 6, 324−324. (15) Song, P. Wet solid method application of phase equilibrium composition for solid-liquid system. J. Salt Lake Res. 1991, 1, 15−23.

1587


Measurement of SolidâLiquid Phase Equilibrium for the Ternary 3

Recommend Documents

Measurement of SolidâLiquid Phase Equilibrium for the Ternary 3