Solubility determination and thermodynamic modeling of 2,4-dinitroaniline in nine organic solvents from T = (278.15 to 318.15) K and mixing properties of solutions

doi:10.1016/j.jct.2016.07.009

The Journal of Chemical Thermodynamics

Volume 102, November 2016, Pages 178-187

https://doi.org/10.1016/j.jct.2016.07.009 Get rights and content

Highlights

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Solubility of 2,4-dinitroaniline in nine organic solvents were determined.
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The solubility were correlated by using four thermodynamic models.
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The mixing properties of solutions were calculated.

Abstract

The solubility of 2,4-dinitroaniline in nine organic solvents of methanol, ethanol, acetone, acetonitrile, n-propanol, toluene, isopropanol, ethyl acetate and 1-butanol was determined experimentally by using the isothermal saturation method over a temperature range from (278.15 to 318.15) K under 101.1 kPa. For the temperature range studied, the solubility of 2,4-dinitroaniline in the solvents increased with a rise of temperature. At a specific temperature, the mole fraction solubility is lowest in toluene, and largest in acetone. The solubility order of 2,4-dinitroaniline is acetone > ethyl acetate > acetonitrile > 1-butanol > ethanol > methanol > (n-propanol, isopropanol) > toluene. The modified Apelblat equation, λh equation, Wilson model and NRTL model were employed to correlate the solubility of 2,4-dinitroaniline in the solvents studied. The maximum values of root-mean-square deviation (RMSD) and relative average deviation (RAD) were 3.76 × 10⁻⁴ and 1.44%, respectively. The values of RAD obtained with the modified Apelblat equation were smaller than those with the other three models for a certain solvent. Generally, the four thermodynamic models were all acceptable for the systems of 2,4-dinitroaniline in these solvents. Furthermore, the mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration ( $γ_{1}^{\infty}$ ) and reduced excess enthalpy ( $H_{1}^{E, \infty}$ ) were computed. The solution process of 2,4-dinitroaniline was spontaneous and endothermic in the solvents. The solubility determined and thermodynamic studies would be very helpful for optimizing the purification process of 2,4-dinitroaniline.

Graphical abstract

Introduction

2,4-Dinitroaniline (CAS No. 97-02-9) is an important industrial chemical. The use of 2,4-dinitroaniline and its derivatives is widely spread in dye, pesticide, biology, and many other fields [1], [2], [3], [4], [5], [6], [7], [8], [9], [10]. In industry, 2,4-dinitroaniline can be prepared by treating 2,4-dinitrochlorobenzene with ammonia [11], [12] or by treating 1,3-dinitrobenzene and potassium permanganate with ammonia [13], [14]. At present, the commercial preparation method of 2,4-dinitroaniline is using 2,4-dinitrochlorobenzene as raw material. Although the yield of 2,4-dinitroaniline is relatively high by this method (90%), the crude product generally contains some unreacted 2,4-dinitrochlorobenzene or 1,3-dinitrobenzene [11], [12], [13], [14], [15]. With the development of industry, the requirements for product purity are becoming higher. The crude 2,4-dinitroaniline restricts its applications in many aspects.

In previous publications, 2,4-dinitroaniline was separated with high purity by using the extraction method [11], [16], [17], nevertheless, the cost of these process is relatively high. It is common sense that crystallization is a significant procedure in purifying a solid compound and solubility is of great importance in designing the industrial crystallization process. To the best of the authors’ present knowledge, crystallization is an effective way to purify 2,4-dinitroaniline. Unfortunately, only the solubility of 2,4-dinitroaniline in water [18], [19] and in mixed solvent of water-pyridine, water-acetonitrile, and water-ethylene glycol have been reported in the literature [20]. Solubility, which is of great significance in the purification procedure of 2,4-dinitroaniline via the method of solvent crystallization, may be used to optimize the design of process crystallization and improve the purity of 2,4-dinitroaniline. Therefore, in order to obtain 2,4-dinitroaniline with high purity, study on the 2,4-dinitroaniline solubility in different solvents and the thermodynamic properties of dissolution is especially necessary.

The purposes of the work are to (1) determine the solubility of 2,4-dinitroaniline in methanol, ethanol, isopropanol, n-propanol, 1-butanol, ethyl acetate, toluene, acetone and acetonitrile at temperatures ranging from (278.15 to 318.15) K by a high performance liquid chromatography (HPLC); (2) correlate the solubility values using the Apelblat equation, λh equation, Wilson model and NRTL model; and (3) compute mixing properties for the dissolution process of 2,4-dinitroaniline in different solvents.

Section snippets

Thermodynamic solubility models

Based on thermodynamic theory, many equations are generally used to study the solid–liquid equilibrium [21], [22], such as the modified Apelblat equation model [23], [24], the Buchowski–Książczak λh equation model [25], Wilson model [26] and NRTL model [27]. In order to find out an appropriate equation to describe the solubility of 2,4-dinitroaniline in different solvents and extend the use of the acquired solubility results. In this work, the four models are employed to correlate the

Materials

2,4-Dinitroaniline with a mass fraction of 0.984 was provided by Beijing Ouhe Chemical Technology Co., Ltd. The crude 2,4-dinitroaniline was crystallized three times in acetone. The mass fraction purity of the recrystallized sample was 0.996, which was confirmed by the high-performance liquid phase chromatograph (Agilent-1260). All the solvents (methanol, ethanol, acetone, acetonitrile, acetic acid, n-propanol, toluene, isopropanol, ethyl acetate and 1-butanol) were of analytical grade. They

Property of the pure component

The determined DSC curve of 2,4-dinitroaniline is shown in Fig. 2. From the results obtained with DSC analysis, the melting temperature T_m and melting enthalpy Δ_fus H of 2,4-dinitroaniline are 451.15 K and 24.81 kJ·mol⁻¹, respectively. The value of T_m determined in the present work is higher than that determined by Szpakiewicz [34], but lower than that determined by Burkhardt [35]. The deviations may be due to difference in equipment, samples and (or) measured conditions [36].

Crystal forms

X-ray diffraction of

Conclusions

In this work, the equilibrium solubility of 2,4-dinitroaniline in nine pure solvents was determined experimentally by using the isothermal saturation method within the temperature range from (278.15 to 318.15) K under 101.1 kPa. With the increase in temperature, the solubility of 2,4-dinitroaniline in the selected solvents increases. At a fixed temperature, they follow the sequence in different solvents: acetone > ethyl acetate > acetonitrile > 1-butanol > ethanol > methanol > (n-propanol, isopropanol) >

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Project number: 21406192) and the Priority Academic Program Development of Jiangsu Higher Education Institutions. The authors would like to express their gratitude for the Practice Innovation Project of Jiangsu Province for Post Graduate Students (Project number: SJZZ15_0180).

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Solubility determination and thermodynamic modeling of 2,4-dinitroaniline in nine organic solvents from T = (278.15 to 318.15) K and mixing properties of solutions

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Thermodynamic solubility models

Materials

Property of the pure component

Crystal forms

Conclusions

Acknowledgments

J. Ind. Eng. Chem.

J. Mol. Catal. A-Chem.

J. Mol. Liq.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Mol. Struct.

J. Chem. Thermodyn.

Secondary mutations correct fitness defects in toxoplasma gondii with dinitroaniline resistance mutations

Genetics

Screening of new 2,4- and 2,6-dinitroaniline derivates for phytotoxicity and antimitotic activity

Cytol. Genet.

Single-stage synthesis of 2,4-dinitroaniline from 1,3-dinitrobenzene

Czas. Tech.