Measurement and correlation of the solubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) in different solvents

doi:10.1016/j.jct.2015.06.003

The Journal of Chemical Thermodynamics

Volume 89, October 2015, Pages 264-269

https://doi.org/10.1016/j.jct.2015.06.003 Get rights and content

Highlights

•
The laser monitoring system was used for measuring the solubilities of DNTF.
•
Three correlation equations were adopted to correlate the experimental values.
•
The three-dimensional figure between ln x_i and 1/T, ln T was obtained.
•
Thermodynamic properties were calculated by the experimental solubilities.

Abstract

A knowledge of the solubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) in different solvents is essential for crystallization and further theoretical studies. The laser monitoring system was used for measuring the solubility of DNTF in methanol, ethanol, acetic acid, benzene, toluene and n-butanol at temperatures ranging from (298.15 to 338.15) K. Polynomial empirical equation, ideal model and modified Apelblat equation were used to correlate the experimental values. The correlated results of three correlation equations present good consistency with the experimental values. In addition, the modified Apelblat equation produced higher accuracy than the polynomial empirical equation and the ideal equation. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated from the experimental values. The solubility values of DNTF and correlation equations from this experiment would be invoked as basic data and models regarding the crystallization process of DNTF.

Graphical abstract

Introduction

The compound 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF, structure shown in figure 1) is a novel energetic material easily synthesized with high density and low sensitivity. Further study shows that its comprehensive property is more superior than octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) but close to 1,2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) [1]. From the study of the crystal structure of DNTF by Zhou et al. [2], we can conclude that the three five-membered rings of DNTF are not coplanar and they form a chair structure in three-dimensional space. Since it is a widely used in explosives and propellants, more attention has been paid by many researchers in recent decades.

Just as with other energetic materials, the morphology and purity play crucial roles in the mechanical strength, sensitivity and application of DNTF. However, the DNTF particles obtained by synthetic reactions [3] have low purity and irregular morphology, so the comprehensive performance [4], [5] of DNTF cannot be shown when used directly. Crystallization is an important and traditional way to enhance the purity and morphology of a solid. In addition, the solubility values are significant for the selection of solvent, which is a crucial step for crystallization. The reagent cannot be used as the solution for crystallization when the solubility changes little with a change of temperature. However, few items exist of solubility values for DNTF [6], so the measurement of the solubility of DNTF in different solvents is important.

In this work, the solubility of DNTF in six organic solvents at temperatures ranging from (298.15 to 338.15) K was measured. Three common correlation equations are adopted to correlate the experimental values. The standard dissolution enthalpy, standard dissolution entropy and standard Gibbs energy are calculated from the experimental results. The ideal solvent for crystallization of DNTF was selected.

Section snippets

Materials

DNTF sample was provided by Xi’an Modern Chemistry Research Institute. The DNTF was purified by recrystallization in alcohol, (acetone + water) solution, respectively, and its mass fraction purity was greater than 0.995. Acetamide, methanol, ethanol, acetic acid, benzene, toluene, and n-butanol of analytical reagent grade were purchased from local reagent factory without further purification whose mass fraction purity were no less than 0.995. Table 1 contains the detailed information of reagents

Reliability detection

Before the measurement of the solubility of DNTF, it was necessary to detect whether our method and apparatus are precise or not by comparing the solubility of acetamide in ethanol measured in this experiment with those in the literature [10]. The literature values and experimental values are exhibited in table 2. Figure 3, drawn according to Table 2, illustrates the comparison. Good consistency is revealed between our experimental values and those in the literature, which demonstrates that the

Conclusions

The solubility of DNTF in different solvents increases with increasing temperature as a non-linear function. Since its solubility in acetic acid, benzene, and toluene change more obviously with the variation of temperature than in methanol, ethanol, and n-butanol, the former are better solvents of DNTF for crystallization than the latter. Moreover, comparing with benzene and toluene, the acetic acid has a series of advantages such as non-toxic, inexpensive, miscibility with water which is the

References (19)

X.H. Shi et al.
Chin. J. Chem. Eng.
(2006)
T. Prapasawat et al.
Fluid Phase Equilib.
(2014)
L.K. Jiang et al.
Fluid Phase Equilib.
(2014)
A. Apelblat et al.
J. Chem. Thermodyn.
(2001)
Y. Zhao et al.
J. Chem. Thermodyn.
(2013)
N. Wang et al.
Fluid Phase Equilib.
(2012)
Y. Hu et al.
J. Mol. Liq.
(2014)
W. Zheng et al.
Chin. J. Energy Mater.
(2006)
Y.S. Zhou et al.
Chin. J. Explos. Propell.
(2005)

There are more references available in the full text version of this article.

Cited by (40)

Premature thermal decomposition behavior of 3,4-dinitrofurazanfuroxan with certain types of nitrogen-rich compounds
2023, Defence Technology
3,4-Dinitrofurazanfuroxan (DNTF), as a high-energy-density material, features good thermal stability and wide applications. This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-rich compounds containing N–H. The thermal stabilities of DNTF and its hybrid systems were investigated using differential thermal analysis/thermogravimetry (TG), vacuum stability test, and accelerating rate calorimetry under isothermal, non-isothermal, and adiabatic conditions, respectively. Results showed that the thermal stability and thermal safety of DNTF significantly decreased after combining with nitrogen-rich compounds containing N–H. Calculation results showed that the activation energy of the DNTF hybrid systems was significantly lower than that of DNTF. The TG-IR was used to monitor the generation of fugitive gases during the thermal decomposition of the DNTF/5-aminotetrazole (5-ATZ) hybrid. Moreover, the nitrogen-rich molecules containing N–H interacted extensively with DNTF, and this interaction accelerated the thermal degradation of DNTF.
Crystallization thermodynamics of 2,4(5)-dinitroimidazole in binary solvents
2023, Chinese Journal of Chemical Engineering
2,4(5)-Dinitroimidazole (2,4(5)-DNI) is an important organic intermediate, and itself can also be used for energetic material. In this work, the solubility of 2,4(5)-DNI in (methanol + water, acetonitrile + water, acetone + water) binary solvents were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 kPa. The Jouyban–Acree model, van’t Hoff–Jouyban–Acree model, Apelblat–Jouyban–Acree model, Ma model, and Sun model were used to correlate the experimental data. The values of relative average deviation (RAD) and root-mean-square deviation (RMSD) were very small, indicating that the error between the experimental value and the correlated value was very small. The thermodynamic parameters such as dissolution enthalpy, dissolution entropy and Gibbs energy were calculated based on solubility data. High-purity of 2,4(5)-DNI was efficiently obtained by using cooling and dilution crystallization method.
Measurement, correlation of solubility and thermodynamic properties of 1,3-dichloro-2,4,6-trinitrobenzene in different mono-solvents
2022, Journal of Chemical Thermodynamics
Citation Excerpt :
In addition, the specific test conditions were as follows: N2 atmosphere with a flow rate of 50 mL·min−1 and a heating rate of 10 K·min−1. The solubility of DCTNB in sixteen mono-solvents were determined by laser dynamic method whose theories and apparatus are described in the literature [23-25], and the method was also validated. The experiment setup for measuring solubility of DCTNB was shown schematically in Fig. 3.
The solubility of 1,3-dichloro-2,4,6-trinitrobenzene (DCTNB) in sixteen mono-solvents (methanol, ethanol, isopropanol, n-butanol, toluene, xylenes, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, acetone, ethyl acetate, acetonitrile, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide) was measured by a laser dynamic method over the temperature range from 298.15 K to 333.15 K under 0.1 MPa. The results show that the solubility of DCTNB increase with increasing temperature in sixteen mono-solvents. Within the experimental temperature range, the average solubility of DCTNB was recorded as the maximum data in N-methylpyrrolidone (29.55 × 10⁻²) and the minimum data in isopropanol (0.26 × 10⁻²). The modified Apelblat equation, Yaws model, van't Hoff equation, λh equation, and new correlative combined model were used to correlate the solubility of DCTNB in sixteen mono-solvents, and the modified Apelblat equation and Yaws model showed satisfactory accordance with the experimental data. Furthermore, the thermodynamic properties of DCTNB dissolution process in the investigated mono-solvents, including standard dissolution enthalpy (9.08 ∼ 47.66 kJ·mol⁻¹), standard dissolution entropy (18.61 ∼ 101.59 J·K⁻¹·mol⁻¹) and standard Gibbs free energy (3.22 ∼ 16.12 kJ·mol⁻¹) were calculated by the van't Hoff and the Gibbs equations. The results demonstrate that the dissolution behavior of DCTNB in sixteen mono-solvents is a non-spontaneous and endothermic process. The solubility data, correlation models, and thermodynamics properties presented in this study would provide essential support for the research of purification and crystallization of DCTNB.
Solubility, Hansen solubility parameter, molecular simulation and thermodynamic analysis of N-methyl-3,4,5-trinitropyrazole at various temperatures
2022, Journal of Molecular Liquids
The solubility of N-methyl-3,4,5-trinitropyrazole (MTNP) in (isopropanol + ethanol) mixtures at T = 283.15 K-323.15 K was tested by a laser monitoring method. The solubility of MTNP increases with the increasing temperature in (isopropanol + ethanol) mixtures. The solubility of MTNP decreases with the increasing isopropanol mass fraction ranging from 0.10 to 0.90. Besides, supersolubility (the metastable zone width) of MTNP was determined by a laser monitoring method. The experimental results showed that the solubility of MTNP in (isopropanol + ethanol) solvent mixtures increases with increasing temperature and the metastable zone width decreases with increasing temperature. Additionally, the values were correlated by the modified Apelblat equation, van’t Hoff equation, CNIBS/R-K model and Ma model. In addition, Hansen solubility parameters were used to explain the solubility order. Solubility order of MTNP in (isopropanol + ethanol) solvent mixtures was interpreted by comparing the interaction energy (E_inter) between MTNP and binary solvent. The apparent thermodynamic properties of Gibbs energy, enthalpy and entropy were calculated by the van’t Hoff and Gibbs equations. The enthalpy-entropy relationship for MTNP was discussed. Finally, solid-liquid surface tension and surface entropy factor were obtained by the solubility data.
Crystallization thermodynamics of 2,4(5)-dinitroimidazole in eleven pure solvents
2022, Chinese Journal of Chemical Engineering
Citation Excerpt :
Solution crystallization is an important means to separate and purify for solid compounds, which is based on the solubility of the target compound in the solvent. Meanwhile, solution crystallization is also used for the purification of energetic materials, such as 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexazaisowurtzitane (CL-20) [19,20], 2,20,4,40,6,60-hexanitrostilbene (HNS) [21,22], 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) [23–25], 1,1-diamino-2,2-dinitroethylene (FOX-7) [26,27], 5,5′-Bistetrazole-1,1′-diolate (TKX-50) [28], 2,4,6-trinitroresorcinol hydrate [29,30], and the like. However, only the solubility of 2,4(5)-DNI in ethanol was reported in the literature [31], and these data cannot meet the requirements for purification of 2,4(5)-DNI.
2,4(5)-Dinitroimidazole (2,4(5)-DNI) is an important energetic material, and it is also an important precursor for the preparation of drugs and energetic materials. In this study, the solubility of 2,4(5)-DNI in eleven pure solvents (chlorobenzene, benzene, 1,2-dichloroethane, toluene, water, isopropyl alcohol, ethyl acetate, acetonitrile, methanol, 1,4-dioxane and acetone) were measured by using a dynamic test method from 278.15 K to 323.15 K under 101.1 kPa. Four solubility models were used to fit the experimental data, which were ideal model, modified Apelblat equation, polynomial empirical equation, and λh equation. Meanwhile, the relative average deviation and root-mean-square deviation between the experimental data and the fitted data were also calculated. Furthermore, the three thermodynamic parameters, i.e., dissolution enthalpy, dissolution entropy and Gibbs energy were obtained based on solubility data. Finally, the crude product of 2,4(5)-DNI was crystallized with acetone as solvent, and the purity of the crystalline product was greater than 99.5%.
Dissolution behavior of 5-fluorouracil in fourteen neat solvents: Solubility, correlation, solvent effect, Hansen solubility parameter, molecular simulation and thermodynamic analysis
2022, Journal of Molecular Liquids
Citation Excerpt :
The molar volume of 5-fluorouracil (Vs) can be obtained from the SciFinder database [11], and the data is 47.6 cm3·mol−1. The solubility of 5-fluorouracil was decided with a laser monitoring [16]. Firstly, accurately measure a certain amount of solvent and weigh a proper excess of 5-fluorouracil into the crystallizer.
A dynamic laser monitoring was used to determined the solubility of 5-fluorouracil at T = (283.15, 288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15 and 323.15) K in 14 solvents, including methanol, water, ethanol, butyric acid, 1-propanol, propionic acid, i-propanol, 1-butanol, acetic acid, i-butanol, formic acid, 1-pentanol, i-amyl alcohol and DMF at P = 0.1 MPa. When the temperature changes from T = (283.15 K − 323.15 K), the solubility values of 5-fluorouracil in 1-butanol, water, ethanol, i-propanol, i-butanol, 1-pentanol, i-amyl alcohol, formic acid, acetic acid, propionic acid, butyric acid, methanol, DMF and 1-propanol were 0.001013–0.003101, 0.001102–0.003452, 0.002022–0.004510, 0.000549–0.002472, 0.000629–0.002615, 0.000791–0.002863, 0.000714–0.002756, 0.000481–0.002382, 0.000413–0.002198, 0.000374–0.002139, 0.000247–0.001427, 0.003130–0.007874, 0.003442–0.014331 and 0.001836–0.004646. It can be seen from the experimental results that the solubility of 5-fluorouracil in all solvents increases with the increase of temperature. Hansen solubility parameter studies the dissolution behavior of 5-fluorouracil in the tested solvents. The Kamlet-Taft parameters were used to discuss the solvent effects. Moreover, the molecular modeling studies were conducted in the paper. Subsequently, the solubility values were corrected by the modified Apelblat equation, Two-Suffix Margules model, NRTL model and Wilson model. Finally, the thermodynamic properties of Gibbs energy, enthalpy and entropy were calculated by the van’t Hoff and Gibbs equations.

View all citing articles on Scopus

View full text

Measurement and correlation of the solubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan (DNTF) in different solvents

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Reliability detection

Conclusions

Chin. J. Chem. Eng.

Fluid Phase Equilib.

Fluid Phase Equilib.

J. Chem. Thermodyn.

J. Chem. Thermodyn.

Fluid Phase Equilib.

J. Mol. Liq.

Chin. J. Energy Mater.

Chin. J. Explos. Propell.