Solid-liquid equilibrium and phase diagram for the ternary (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) system

https://doi.org/10.1016/j.jct.2016.06.011Get rights and content

Highlights

  • Solubility for 2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane were measured.

  • Three isothermal phase diagrams were plotted based on solubility data.

  • Experimental solubility data were correlated by NRTL and Wilson models.

Abstract

In this research, solid-liquid equilibrium for the ternary system (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) was measured at 283.15 K, 293.15 K and 303.15 K, respectively. Three isothermal phase diagrams of the system were plotted using the values of the experimental solubility. Pure 2-naphthaldehyde and o-phthalic anhydride were formed at (283.15, 293.15 and 303.15) K, and were determined by Schreinemaker’s wet residue method. The crystallization region of o-phthalic anhydride was found to be much larger than that of 2-naphthaldehyde at a certain temperature. The experimental solubility at multiple temperatures was correlated by the NRTL and Wilson models. The NRTL model was more accurate than the Wilson model in this system. The diagram of density versus component was also constructed.

Introduction

2-Naphthaldehyde (CAS NO: 66-99-9) is an important chemical intermediate. It is widely used in pharmaceuticals, dyestuffs, flavours and fragrance materials, and extensively to adjust the growth of the plant [1], [2]. Traditionally, 2-naphthaldehyde is mainly synthesized by oxidation using oxidants such as chromium oxides and hydrogen peroxide. But there exist some insufficiency in this process [1], [2], [3], [4], [5]. Recently, our research team used molecular oxygen to catalytic oxidize 2-methylnaphthalene to 2-methy-1,4-naphthoquinone in the presence of composited vanadium in the vapour phase and some achievements had been scored [3], [4], [5], [6]. It is a series of complex high exothermic processes with phthalic anhydride, 2-naphthaldehyde and other by-products. Therefore isolation and purification are essential for getting pure 2-naphthaldehyde from its compounds.

The solid-liquid equilibrium is known as the basis for crystallization which is an effective method in isolation and purification for a mixture [7], [8], [9]. Besides, the solid-liquid phase diagram also play an important role in the isolation and purification process [10], [11]. To separate 2-naphthaldehyde from the crude mixture, it is necessary for us to have knowledge of their solid-liquid equilibrium. The solubility of 2-naphthaldehyde in several common organic solvents had been reported [2]. However, the mutual solubility of ternary (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) system has not been recorded in the previous literature. The main purpose of this research is to study the solid-liquid equilibrium for ternary (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane system) at different temperatures and construct the phase diagrams based on the phase equilibrium data.

In this study, the Schreinemakers’ wet residue method [12], [13], [14] was employed to construct the ternary phase diagrams of the (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) system at different temperatures. When the equilibrium of the ternary system was reached, there exist at least one solid phase and one liquid phase. The pure phase could be obtained and further analysed. But it was difficult for us to obtain the pure solid phase without a little mother liquor. According to the Schreinemaker wet residue method, joining the composition of the pure solid and the saturated liquid in equilibrium, a tie line will be obtained, and the compound point including wet solid must fall within it. Varying the ratio of the mixture, we would obtain a series of tie lines representing the saturated liquid and wet solid phase. These tie lines have a common point that represents the pure solid phase.

Section snippets

Materials

2-Naphthaldehyde with a mass fraction of 0.998 was supplied by Aladdin Chemical Reagent Co., Ltd., China; o-phthalic Anhydride was supplied by Kermel Tianjin Chemical Reagent Co., Ltd., China, with mass fraction purity higher than 0.997. The 1,4-dioxane, with mass fraction purity higher than 0.997, was provided by Kermel Tianjin Chemical Reagent Co., Ltd., China. Benzoic acid was also supplied by Kermel Tianjin Chemical Reagent Co., Ltd., China, with mass fraction purity greater than 0.995.

Solid-liquid equilibrium models

In the solid-liquid equilibrium system with a constant temperature and pressure, the liquid fugacity is equal to solid fugacity. For a given component A, this state is expressed as:xASγASfAS=xALγALfAL

Here S and L denote the solid and liquid conditions, respectively; xA is the mole fraction of component A, γA signifies the activity coefficient and fA represents the fugacity.

In terms of the classical theory of solid-liquid phase equilibrium, the solubility equation can be derived and expressed as

Solid-liquid phase equilibrium results

To check on the reliability of the measurement, the solubility of benzoic acid in water was measured at different temperatures. The experimental values were contrasted with the data reported in the literature [26]. The literature values and the corresponding experimental values are listed in Table 2, and the result is shown in Fig. 2. The experimental results agree well with the literature data.

The solid-liquid phase equilibrium values for the (ternary 2-naphthaldehyde + o-phthalic anhydride + 

Conclusions

The solid-liquid equilibrium for the ternary (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) system at different temperatures was determined experimentally. Three ternary phase diagrams were mapped based on the solubility reshults. Each solubility phase diagram contained three crystallization regions (2-naphthaldehyde, o-phthalic anhydride, and a mixture of 2-naphthaldehyde and o-phthalic anhydride), two equilibrium solubility curves and one invariant point. The two pure solid phase

Acknowledgment

We thank the Henan Province Science and Technology Bureau, China (Project number: 114200510005).

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