Fluid Phase Equilibria 383 (2014) 27–31 Solid–liquid equilibrium of ternary system sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfonate + water at (283.15, 303.15 and 323.15) K Rongrong Li a,b,*, Guobo Huang a, Huanan Hu a, Chenghong Li a, Wenping Jia a,** a Institute of Applied Chemistry, Taizhou University, Linhai, Zhejiang 317000, PR China b Industrial Catalysis Institute of Zhejiang, University of Technology, Hangzhou 310014, PR China A R T I C L E I N F O Article history: Received 27 April 2014 Received in revised form 12 September 2014 Accepted 24 September 2014 Available online 28 September 2014 Keywords: Sodium naphthalenesulfonate Phase equilibria NRTL Schreinemaker A B S T R A C T In this work, solid–liquid equilibria (SLE) data for ternary sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfonate + water system was measured at (283.15, 303.15 and 323.15) K respectively. The diagrams for solid liquid phase of the ternary system were well-established by the measured solubility data. The solid phases formed in the studied system were determined by the method of Schreinemaker’s wet residue. Moreover, the density of equilibrium liquid phase was gained in the process. At each temperature, there are two pure solids forming. They are sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate in the ternary system. The solubility data for the ternary system were calculated and regressed by NRTL model, giving acceptable results for the investigated systems. ã 2014 Elsevier B.V. All rights reserved. Contents lists available at ScienceDirect Fluid Phase Equilibria journal homepage: www.elsevier .com/ locate /fluid 1. Introduction Sodium 1-naphthalenesulfonate (CAS Registry No. 130-14-3) is a valuable regent which is widely used in the functionalized reduced graphene oxide stabilization of silver nanoparticles [1]. Meanwhile, this is an intermediate in the manufacturing of 8-Anilino-1-naphthalenesulfonate [2] and 8-p-toluidino-1- naphthalenesulfonate [3], and in many other applications. While sodium 2-naphthalenesulfonate (CAS registry no. 532-02-5) is a critically important intermediate which is used as a reactant in the production of 2-naphthol [4]. Sodium 1- and 2-naphthalenesul- fonate are mainly synthesized by the sulphonation of naphthalene with concentrated sulfuric acid, and then condensation by NaCl. The products which were formed by this method included sodium 1- and 2-naphthalenesulfonates in various proportions. They were obtained through sulphonation and condensation respectively. It is very important to purify sodium 1- and 2-naphthalenesulfonates via crystallization in solvent. Some studies used the method of ion exchange process to separate sodium 1-naphthalenesulfonate * Corresponding author at: School of Pharmaceutical and Chemical Engineering, Taizhou University, School of Pharmaceutical and Chemistry, Linhai, Zhejiang, PR China. Tel.: +86 576 85486698. ** Corresponding author. E-mail address:
[email protected] (R. Li). 0378-3812/$ – see front matter ã 2014 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.fluid.2014.09.026 from the b-salt mother liquor [5]. and the method of gel permeation chromatography to fractionate the condensates of sodium 2-naphthalenesulfonate and formaldehyde [6]. We found that sodium 1-naphthalenesulfonate and sodium 2-naphthalene- sulfonate can be easily obtained when water as a solvent in purification. Therefore, the present work is concerned with a systematic determination of the solubility of sodium 1-naphtha- lenesulfonate and sodium 2-naphthalenesulfonate in water. The optimization of process conditions is closely related to the solubility of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate in water. It is significant to study the system and construct the phase diagram of the ternary sodium 1-naphthalenesulfonate–sodium 2-naphthalenesulfonate–water system to improve the separation process. In crystallization process, the solid–liquid phase equilibrium data are very important. Although the solubility of the binary systems sodium 1-naphthalenesulfonate–water and sodium 2-naphthalenesulfonate–water was determined and the corre- sponding binary phase diagrams were constructed [7–9], no studies have been made on the SLE phase diagram of the ternary sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfo- nate + water system. The objective of this research is to investigate and generate the phase diagrams of the ternary system at (283.15, 303.15 and 323.15) K by the method of Schreinemakers’ wet residues and indicate the temperature influence of the ternary system [10–13]. http://crossmark.dyndns.org/dialog/?doi=10.1016/j.fluid.2014.09.026&domain=pdf mailto:
[email protected] http://dx.doi.org/10.1016/j.fluid.2014.09.026 http://dx.doi.org/10.1016/j.fluid.2014.09.026 http://www.sciencedirect.com/science/journal/03783812 www.elsevier.com/locate/fluid Table 1 Purities and suppliers of chemicals. a Compound Mass fraction purity Sources Purification method Analytical method Melting point Tm (K) Melting enthalpies DfusH (kJ mol�1) Sodium 1- naphthalenesulfonate 0.995 Aladdin Chemical Co., Ltd. (China) None HPLC 383.41 22.15 Sodium 2- naphthalenesulfonate 0.995 Aladdin Chemical Co., Ltd. (China) None HPLC 445.85 15.43 a Standard uncertainties u are u(Tm) = 0.03 K, u(DfusH) = 0.04 kJ mol. 28 R. Li et al. / Fluid Phase Equilibria 383 (2014) 27–31 2. Experimental 2.1. Materials Sodium 1- and 2-naphthalenesulfonates are gained by Aladdin Chemical Co., Ltd., with a mass fraction of 0.995, and used without further purification. The purity of these materials was determined by HPLC (high performance liquid chromatog- raphy). Their melting temperatures and enthalpies of fusion were measured using DSC (Netzsch DSC 204F1), which were close to the reported data in cited references [14,15]. The water was twice distilled water (conductivity Table 3 Mass fraction solubility of the ternary sodium 1-naphthalenesulfonate (1) + sodium 2-naphthalenesulfonate (2) + water (3) system at 303.15 K, 101.3 kPa. a Liquid phase Wet solid phase Density of liquid phase (g mL�1) Solid phase 100w1 100w2 100w1 100w2 0 4.86 0 50.35 1.0077 M 1.78 4.60 1.14 32.73 1.0114 M 3.54 4.25 2.61 29.44 1.0145 M 5.64 3.90 5.44 31.07 1.0202 M 7.62 3.43 3.61 39.24 1.0293 M 9.76 3.49 5.82 42.63 1.0436 M 11.45 3.31 8.05 32.83 1.0572 M 13.67 3.21 23.70 25.35 1.0789 M + N 14.14 2.11 27.48 1.84 1.0610 N 14.49 0.98 30.86 0.85 1.0535 N 14.75 0 70.36 0 1.0481 N aW, mass fraction; M, sodium 2-naphthalenesulfonate; N, sodium 1-naphthalenesulfonate. Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.01 kPa, ur(w) = 0.02, and the combined expanded uncertainty Uc is Uc(r) = 0.0005 g mL-1 (0.95 level of confidence). R. Li et al. / Fluid Phase Equilibria 383 (2014) 27–31 29 activity coefficient for a constituent i is showed as lng i ¼ S N j¼1tjiGjixj S N i¼1Gijxi þ SNj¼1 xjGij S N i¼1Gijxi tij � S N i¼1xitijGij S N i¼1Gijxi 2 4 3 5 (4) Gij and tj are NRTL model parameters which need to be determined by follows: Gji ¼ exp �ajitji � � (5) tji ¼ gij � gjj RT (6) aij ¼ aji (7) Dgij(= gij� gjj) and Dgji(= gji� gii) are the cross-interaction energy parameters (J mol�1) which are considered as temperature independent and might be regressed from experimental data. a is the parameter related to the non-randomness in the mixture and varies from 0.2 to 0.47. 4. Results and discussion The density (r) and the solubility data of the liquid phase for the ternary sodium 1-naphthalenesulfonate + sodium 2-naphthalene- sulfonate + water system at (283.15, 303.15 and 323.15) K are expressed in Tables 2–4 respectively. The ternary phase diagrams are demonstrated in Figs. 1–3. Table 4 Mass fraction solubility of the ternary sodium 1-naphthalenesulfonate (1) + sodium 2-n Liquid phase Wet solid phase 100w1 100w2 100w1 100w2 0 10.05 0 62.42 2.10 9.00 1.28 26.74 5.37 8.08 4.82 19.46 7.56 6.96 5.10 34.60 10.18 7.10 9.43 14.96 13.15 6.13 10.44 27.65 15.56 5.70 14.07 13.02 18.83 5.46 44.49 9.68 18.98 4.42 48.01 2.83 19.12 2.99 43.02 2.01 19.55 1.40 39.44 1.06 20.03 0 76.22 0 a W, mass fraction; M, sodium 2-naphthalenesulfonate; N, sodium 1-naphthalenesulfo combined expanded uncertainty Uc is Uc(r) = 0.0005 g mL�1 (0.95 level of confidence). In the phase diagrams as demonstrated in Figs. 1–3, the points W,M, and N represent water, sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate respectively. E1, E2, and E3 represent the solubility of sodium 1-naphthalenesulfonate in water at (283.15, 303.15 and 323.15) K; S1, S2 and S3 represent the solubility of sodium 2-naphthalenesulfonate in water at (283.15, 303.15 and 323.15) K. From Figs. 1–3, we can see that along the solubility curve E1C1, E2C2 or E3C3, there are saturation curves corresponding to the solid-phase sodium 1-naphthalenesulfonate at (283.15, 303.15 and 323.15) K respectively. When we linked the component points of the liquid phase and wet solid phase, then extended, the line is close to the solid-phase of sodium 1-naphthalenesulfonate. Similarly, along the solubility curve S1C1, S2C2 or S3C3, saturation curves correspond to the solid-phase of sodium 2-naphthalenesulfonate. C1, C2 and C3 are invariant point represent the cosaturated solution of the solid phases sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate at different temperatures. In the phase diagrams as shown in Figs. 1–3, there are four regions divided by two solubility curves. The regions in the phase diagram are denoted as follows: I (E1WS1C1 in Fig. 1, E2WS2C2 in Fig. 2, and E3WS3C3 in Fig. 3), unsaturated region; II (E1MC1 in Fig. 1, E2MC2 in Fig. 2, and E3MC3 in Fig. 3), crystalline region of sodium 1-naphthalenesulfonate; III (S1NC1 in Fig. 1 and S2NC2 in Fig. 2, and S3NC3 in Fig. 3), crystalline region of sodium 2-naphthalenesulfonate; IV (NMC1 in Fig. 1, NMC2 in Fig. 2, and NMC3 in Fig. 3), crystalline region of solids sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate. aphthalenesulfonate (2) + water (3) system at 323.15 K, 101.3 kPa. a Density of liquid phase (g mL�1) Solid phase 1.0084 M 1.0157 M 1.0281 M 1.0358 M 1.0570 M 1.0834 M 1.1155 M 1.1735 M + N 1.1436 N 1.1275 N 1.1107 N 1.1002 N nate. Standard uncertainties u are u(T) = 0.02 K, u(p) = 0.01 kPa, ur(w) = 0.02, and the 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 IV III II C1 S1 E1 I mass fracti on m as s f ra ct io n W N M Fig. 1. Phase diagram for the ternary sodium 1-naphthalenesulfonate–sodium 2-naphthalenesulfonate–water system at 283.15 K; W, water; M, sodium 2-naphthalenesulfonate; N, sodium 1-naphthalenesulfonate; C1, cosaturated point of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate; E1, solubility of sodium 2-naphthalenesulfonate in water; S1, solubility of sodium 1-naphthalenesulfonate in water; – calculate values. 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 C2 S2 E2 II mass fractio n N M IV III IW m as s fr ac tio n Fig. 2. Phase diagram for the ternary sodium 1-naphthalenesulfonate–sodium 2-naphthalenesulfonate + water system at 303.15 K; C2, cosaturated point of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate; E2, solubility of sodium 2-naphthalenesulfonate in water; S2, solubility of sodium 1-naphthalene- sulfonate in water; W, N and M have the same meaning as described in Fig. 1, – calculate values. 30 R. Li et al. / Fluid Phase Equilibria 383 (2014) 27–31 Figs. 1–3 further illustrate the temperature dependence of the phase diagram for the ternary sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfonate + water system. When the tem- perature increases from 283.15 K to 323.15 K, the solubility of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfo- nate in water increases significantly, and the invariant point moves upward. The diagram at 283.15 K was close to others diagram. 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 C3 S3 E3 mass fracti on m as s fr ac tio n N W I II III IV M Fig. 3. Phase diagram for the ternary sodium 1-naphthalenesulfonate–sodium 2- naphthalenesulfonate + water system at 323.15 K; C3, cosaturated point of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate; E3, solubility of sodium 2-naphthalenesulfonate in water; S3, solubility of sodium 1-naphthalene- sulfonate in water; W, N and M have the same meaning as described in Fig. 1, – calculate values. On the basis of data collected in Tables 2–4, the relationship between the density of the equilibrium liquid phase and the sodium 2-naphthalenesulfonate concentration values shown in mass fraction (Fig. 4) is gained. The density of equilibrium liquid phase depends on total content of sodium 2-naphthalenesulfo- nate and sodium 1-naphthalenesulfonate. Fig. 4 illustrates the minimum density point corresponding to the lowest total content of sodium 2-naphthalenesulfonate and sodium 1-naphthalene- sulfonate, and the maximum observed in the density values correspond to the maximum total mass of sodium 1-naphtha- lenesulfonate and sodium 2-naphthalenesulfonate. The inflection points which is the intersection point of two solubility curves in Fig. 4 correspond to the cosaturated point C1 in Fig. 1, C2 in Fig. 2 and C3 in Fig. 3. Considering the thermal stability of these compounds, the melting properties were measured by the conventional calori- metric test. The measured melting point and melting enthalpy is also shown in Table 1. The ternary solid–liquid phase equilibrium for the system of sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfonate + water at different tempera- ture is calculated on the basis of the regressed NRTL binary interaction parameters. Here the interaction parameters of sodium 1-naphthalenesulfonate–water and sodium 2-naphtha- lenesulfonate–water were regressed by multidimensional unconstrained nonlinear minimization using MATLAB software based on the solubility of sodium 1-naphthalenesulfonate in water and sodium 2-naphthalenesulfonate in water. The interaction parameters between sodium 1-naphthalenesulfo- nate and sodium 2-naphthalenesulfonate were regressed according to the solubility data of the ternary system of sodium 1-naphthalenesulfonate + sodium 2-naphthalenesul- fonate + water at different temperatures. The regressed param- eters are listed in Table 5, and the calculated solubility is plotted in Figs. 1–3. It can be seen that the evaluated solubility agree well with the experiment value for the studied system. 0.00 0.08 0.16 1.05 1.12 1.19 Mass fraction of sodium 1-naphthalenesulfonate( wt) D en si ty /g m l-1 283.15 K 303.15 K 323.15 K Fig. 4. Density value-composition relationship diagram for the ternary sodium 1-naphthalenesulfonate–sodium 2-naphthalenesulfonate + water system at 283.15 K, 303.15 K and 323.15 K: (&), experimental data point; – experimental relationship diagram. Table 5 The regressed binary interaction parameters Dgij of the NRTL models for the ternary sodium 1-naphthalenesulfonate (1) + sodium 2-naphthalenesulfonate (2) + water (3) system. i–j Dgij aij 1–2 1247.22 0.3 2–1 �2576.69 1–3 �547.52 0.3 3–1 �2944.25 2–3 896.14 0.3 3–2 �1777.58 R. Li et al. / Fluid Phase Equilibria 383 (2014) 27–31 31 5. Conclusions The solid–liquid equilibrium (SLE) phase diagrams and the solubility data for the ternary sodium 1-naphthalenesulfonate + sodium 2-naphthalenesulfonate + water system at (283.15, 303.15 and 323.15) K were determined experimentally. The corresponding solid liquid phase diagrams were obtained as well as the densities of equilibrium liquid phase. The solid phase was affirmed by method of Schreinemaker’s wet residues. Two solid phases were formed in the ternary sodium 1-naphthalenesulfo- nate + sodium 2-naphthalenesulfonate + water system at (283.15, 303.15 and 323.15) K, which were sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfonate. There are three crystalliza- tion fields at temperature of (283.15, 303.15 and 323.15) K, two univariant curves and one invariant point in the phase diagram. According to the phase diagram, pure sodium 1-naphthalenesul- fonate and sodium 2-naphthalenesulfonate can be formed in the solvent of water. The solubility data and the ternary phase diagrams for the system sodium 1-naphthalenesulfonate + sodium 2-naphthalene- sulfonate + water at (283.15, 303.15 and 323.15) K can provide the fundamental basis for preparation of sodium 1-naphthalenesul- fonate and sodium 2-naphthalenesulfonate from the mixtures of sodium 1-naphthalenesulfonate and sodium 2-naphthalenesulfo- nate. At (283.15, 303.15 and 323.15) K, the ternary phase diagram for solid–liquid phase equilibrium data was regressed based on the NRTL model which gives appropriate results for the investigated systems. Acknowledgements The project was supported by the Natural Science Foundation of Zhejiang Province, China(LQ12B03003), Science and Technology Plan Project of Zhejiang Province (2012C37028, 2011C37055), Science and Technology Plan Project of Taizhou (102XCP08). Appendix A. Supplementary data Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.fluid.2014.09.026. References [1] X. Cai, S. Tan, A. Yu, J. Zhang, J. Liu, W. Mai, Z. Jiang, Chem. Asian J. 7 (2012) 1664–1670. [2] T. Considine, H. Singh, H.A. Patel, L.K. Creamer, J. Agric. Food Chem. 53 (2005) 8010–8018. [3] P.M. Horowitz, S. Bowman, Anal. Biochem. 165 (1987) 430–434. [4] V. P. Rusov, V. A. Livanov, S. M. 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