Solubility determination and modelling of 4-nitro-1,2-phenylenediamine in eleven organic solvents from T = (283.15 to 318.15) K and thermodynamic properties of solutions
Graphical abstract
Introduction
4-Nitro-1,2-phenylenediamine (CAS REG No. 99-56-9) is an important organic intermediate. It is widely used in the field of fine chemicals such as dyes, herbicides, pesticides, pharmaceuticals and pigments [1], [2], [3], [4], [5], [6], [7], [8], [9], [10]. For example, it can be used as a raw material to synthesize 6-amino-5-bromoquinoxaline [9] and 5-bromo-6-isothiocyanatoquinoxaline [9]. In particular, it is well known to be enhanced in mutagenic potency by intact plant cells and that is beneficial to detect alpha-keto acids in blood as a reagent [10], [11]. So far, many literatures have reported the synthetic methods of 4-nitro-1,2-phenylenediamine [3], [4], [5], [6], [7], [12], [13], [14], [15], [16]. The 4-nitro-1,2-phenylenediamine is commonly prepared by reacting of 2,4-dinitroaniline with concentrated ammonium sulfide in ethanol solution (95%, mass fraction). The synthesis route is shown in the Fig. 1. During the synthesis process of 4-nitro-1,2-phenylenediamine, it is inevitably accompanied by the formation of by-product 2-nitro-1,4-phenylenediamine [3], [10], [12]. The crude product 4-nitro-1,2-phenylenediamine containing 2-nitro-1,4-phenylenediamine restrains its further applications in many fields. In addition, requirements for the purity of products are increasingly becoming higher with the rapid development of a fine chemical industry. In order to obtain products with high purity, the separation of 4-nitro-1,2-phenylenediamine from the isomer mixtures is a rather important step in the whole process.
It is known that solvent crystallization is an important unit operation that is commonly used as a separation and purification step in the production process. The solid solubility in different solvents is an important physicochemical property which plays a significant role for understanding the (solid + liquid) equilibrium (SLE) or phase equilibrium in the development of a crystallization process. More importantly, solubility is an important physicochemical property which has a significant influence in industrial crystallization processes. According to the previous works [10], [13], [14], solvent crystallization has been reported to purify the 4-nitro-1,2-phenylenediamine directly with high purity. The knowledge of accurate solubility is required for the design of the crystallization process of 4-nitro-1,2-phenylenediamine. In order to obtain high purity product, the knowledge of solubility of 4-nitro-1,2-phenylenediamine in various solvents at elevated temperatures is a critical step and thermodynamic properties of solution are always basic design foundations of chemical separation which can also improve the purity and yield of 4-nitro-1,2-phenylenediamine. To the best of the authors’ present knowledge, no solubility values are reported in the previous works.
The purification of 4-nitro-1,2-phenylenediamine is commonly done using organic solvents. From many species of organic solvents, we chose eleven commonly used organic solvents (methanol, ethanol, n-propanol, isopropanol, acetone, 2-butanone, acetonitrile, ethyl acetate, n-butanol, toluene and 1,4-dioxane) in industrial purification process. The main objectives of this work are to (1) determine the solubility of 4-nitro-1,2-phenylenediamine in the eleven solvents at temperatures ranging from (283.15 to 318.15) K under atmosphere pressure; (2) correlate the solubility with the modified Apelblat equation, λh equation, Wilson model and NRTL model; and (3) evaluate the mixing properties for the solution process of 4-nitro-1,2-phenylenediamine in different solvents. Because temperature of solvent-assisted crystallization of 4-nitro-1,2-phenylenediamine lies close to the temperature range 280 K to 320 K, the selected temperatures of this study are within the range from T = 283.15 K to T = 318.15 K.
Section snippets
Solubility models
In order to determine an appropriate equation or model to describe the solubility behaviour of 4-nitro-1,2-phenylenediamine in the selected solvents and achieve further application for the solubility results obtained in this work, four thermodynamic models are employed to correlate the solubility of 4-nitro-1,2-phenylenediamine in the selected solvents. These are the modified Apelblat equation [17], [18], [19], λh equation [20], Wilson model [21] and NRTL model [22].
Materials and apparatus
4-Nitro-1,2-phenylenediamine was provided by Beijing HWRK Chemical Co., Ltd, China with a mass fraction of 0.982. It was recrystallized three times in ethyl acetate. The purified 4-nitro-1,2-phenylenediamine had a purity of 0.997 in mass fraction, which was determined by a high-performance liquid phase chromatograph (HPLC, Agilent-1260). The selected solvents, such as methanol, ethanol, n-propanol, isopropanol, acetone, 2-butanone, acetonitrile, ethyl acetate, n-butanol, toluene and 1,4-dioxane
Properties of pure substance
The DSC curve of 4-nitro-1,2-phenylenediamine is shown in Fig. 3. Based on the DSC analysis results, the melting temperature Tm and melting enthalpy ΔfusH of 4-nitro-1,2-phenylenediamine are 472.40 K and 36.28 kJ·mol−1. The value of Tm determined in this work is lower than that reported in Ref. [29], but within the range determined by Borsche [30] and Milos [31]. The deviations may be due to the difference in equipment, samples and (or) measuring conditions.
On the basis of the melting enthalpy Δ
Conclusions
The mole fraction solubility of 4-nitro-1,2-phenylenediamine in eleven organic solvents including methanol, ethanol, n-propanol, isopropanol, acetone, 2-butanone, acetonitrile, ethyl acetate, n-butanol, toluene and 1,4-dioxane was determined experimentally by using the isothermal saturation method at temperatures ranging from (283.15 to 318.15) K under 101.2 kPa. The mole fraction solubility of 4-nitro-1,2-phenylenediamine increases with increasing temperature in the selected solvents. At a
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