Article pubs.acs.org/jced
Solubilities of Dihydroxylammonium 5,5′-Bistetrazole-1,1′-diolate in Various Pure Solvents at Temperatures between 293.15 and 323.15 K Chunyuan Zhang,† Shaohua Jin,† Shusen Chen,† Yan Zhang,† Liang Qin,‡ Xiaochun Wei,‡ and Qinghai Shu*,† †
School of Material Science and Engineering, Beijing Institute of Technology, Beijing 100081, People’s Republic of China Research Institute of Gansu Yinguang Chemical Industry Group, Baiyin 730900, People’s Republic of China
‡
ABSTRACT: The solubility of newly insensitive energetic material dihydroxylammonium 5,5′-bis(tetrazole)-1,1′-diolate (TKX-50) was measured in ethyl acetate, ethanol, deionized water, dimethyl fumarate (DMF), formic acid, toluene, and dimethyl sulfoxide (DMSO) between 293.15 and 323.15 K at atmospheric pressure by the gravimetric method, which is increased with an increase of temperature. The order of the solubility is ethyl acetate < ethanol < toluene < deionized water < DMF < formic acid < DMSO. The experimental mole fraction solubility data were correlated with a simple Apleblat equation, showing a good fitting between the experimental data and Apleblat equation.
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INTRODUCTION Dihydroxylammonium 5,5′-bis(tetrazole)-1,1′-diolate (TKX-50, C2N10O4H8, colorless crystal, Figure1) is a novel explosive of
experimental data was correlated with a simple Apleblat equation.
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EXPERIMENTAL SECTION Chemicals. TKX-50 was homemade and purified according to the literature1 with apurity of 99.8% as determined by highperformance liquid chromatography (HPLC). Ethyl acetate, ethanol, DMF, formic acid, toluene, and DMSO were all analytical grade and purchased from suppliers without further purification; deionized water (18 MΩ·cm−1) was obtained from a Milipore Mili-Q Plus water system (Table 1). Procedure. Although HPLC method has been used for determination of the solubility of explosives,9−11 the UV−vis absorption of TKX-50 is very low. In this work, the gravimetric method12 was used to study the solubility of TKX-50 in ethyl acetate, ethanol, deionized water, DMF, formic acid, toluene, and DMSO. An excess mass of solid TKX-50 was added to glass vials containing 100 mL of the solvents. Then the vials were incubated in a temperature thermostatic reaction with magnetic stirring water bath at temperatures of 293.15, 298.15, 303.15, 308.15, 313.15, 318.15, and 323.15 K. The temperature was determined using a pure solvent bottle with a thermometer inside. The temperature fluctuation of the water bath was controlled below ±0.5 K, and the temperature of thermostatic reaction was calibrated by thermometer with precision of 0.1 K. After the dissolution equilibrium of TKX-50 with another 12 h standing at the corresponding temperature, 3 × 20 mL (3 × 50 mL for ethyl acetated and ethanol) of the sample solution was transferred by a
Figure 1. Chemical structure of TKX-50.
high energy and low sensitivity that was synthesized in 2013 by Niko Fischer.1 It has similar detonation velocity as high as CL-20 but lower sensitivity (both mechanically and thermally) than commonly used high energy explosives such as RDX, HMX, and CL-20, making increased margins of safety in application, indicating that TKX-50 could be used as one promising insensitive high energetic material in explosives and propellants.2−4 Generally, the explosive properties of a high energy compound are significantly influenced by its purity.5−7 To achieve higher purity, the most commonly used means is recrystallization where the solid−liquid equilibrium is of paramount importance for the design of processes, especially antisolvent crystallization.8 Therefore, the solubility study of TKX-50 in different solvents to obtain the thermodynamic parameters is very urgently needed. In this work, the solubility of TKX-50 in ethyl acetate, ethanol, deionized water, DMF, formic acid, toluene, and DMSO has been determined over a temperature range of 293.15−323.15 K by a gravimetric method at atmospheric pressure, and the © XXXX American Chemical Society
Received: January 5, 2016 Accepted: April 15, 2016
A
DOI: 10.1021/acs.jced.6b00009 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
Table 1. Information of Chemicals Used in This Worka chemical name toluene DMF formic acid DMSO ethanol ethyl acetate deionized water TKX-50
source Beijing Chemical Reagent Co., Ltd. Beijing Chemical Reagent Co., Ltd. Beijing Chemical Reagent Co., Ltd. Beijing Chemical Reagent Co., Ltd. Beijing Chemical Reagent Co., Ltd. Beijing Chemical Reagent Co., Ltd. our laboratory our laboratory
mass fraction purity
analysis method
≥0.99
GC
purification method none
Apelbalt
≥0.99
GC
none
≥0.98
GC
none
≥0.99
GC
none
≥0.99
GC
none
≥0.99
GC
none
≥0.99
None
none
HPLC
recrystallization
0.998
Table 2. Measured Mole Fraction Solubilities (xi), calculated Mole Fraction Solubilities (xcal), and Relative Deviation (δ) of TKX-50 in Different Studied Solvents at Different Temperatures at 0.1 MPaa solvent
T/K
(105) xi
(105) xcal
100 δ
deionized water
293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15 293.15 298.15 303.15 308.15 313.15 318.15 323.15
2.416 2.828 3.289 3.592 4.174 4.835 5.501 6.376 7.178 9.564 14.23 18.30 22.50 26.92 21.31 23.09 25.03 27.96 30.23 34.65 39.24 1.847 2.200 2.443 2.597 2.895 3.236 3.686 122.1 130.6 149.1 159.1 179.0 191.2 211.1 0.3873 0.4823 0.5918 0.7187 0.8156 0.9643 1.213 0.1933 0.2159 0.2374 0.2718 0.3160 0.3564 0.3919
2.456 2.806 3.208 3.670 4.201 4.810 5.509 6.280 7.430 9.845 14.399 17.79 21.93 27.75 20.58 22.86 25.38 28.17 31.27 34.69 38.44 1.892 2.124 2.377 2.653 2.951 3.275 3.624 120.9 133.3 146.8 161.1 176.6 193.2 210.8 0.3977 0.4801 0.5783 0.6949 0.8333 0.9972 1.191 0.1897 0.2148 0.2431 0.2748 0.3146 0.3504 0.3951
−1.63 0.78 2.46 −2.19 −0.66 0.52 0.15 1.50 −3.51 −2.94 −1.16 2.78 2.53 −3.10 3.43 1.00 −1.39 −0.79 −3.45 −0.12 0.20 −3.12 3.29 2.11 2.16 −1.95 −1.20 1.68 0.9 −2.14 1.59 −1.27 1.34 −0.73 0.11 −2.68 0.46 2.29 3.31 −2.17 −3.41 1.82 1.86 −0.50 −2.40 −1.12 1.76 1.70 −0.81
DMF
a
GC, gas chromatography; HPLC, high-performance liquid chromatography.
syringe into a dried weighted bottle with a weight of m0 (balance precision 0.01 mg). The vials, containing the sample, were quickly and tightly closed and weighted as m1 with balance precision 0.01 mg. After the solution is completely dried under nitrogen, the weight of the vials containing the residue was measured again as m2. All of the experiments were carried out three times simultaneously and analyzed. Thus, the mole fraction x of the solute could be calculated according to the following equation. x=
m 2 − m0 M1 m 2 − m0 m −m + 1M 2 M1 2
formic acid
toluene
(1)
where M1 and M2 are the molecular weights of solute and solvent, respectively.
DMSO
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RESULTS AND DISCUSSION Solution. The solubility of TKX-50 in ethyl acetate, ethanol, deionized water, DMF, formic acid, toluene and DMSO in the range of 293.15 to 323.15 K was given in Table 2, revealing that the order of solubility is ethyl acetate < ethanol < toluene < deionized water < DMF < formic acid < DMSO. The linear relationship between temperature and solubility of TKX-50 in different solvents was obtained, suggesting that the mole fraction solubility of TKX-50 was found to increase with the increase of temperature in all of pure solvents. Considering the solubility of TKX-50 in DMF showed the strongest dependency on temperature, and the solubility of TKX-50 in DMSO is much higher than that in other solvents in the investigated temperature range, DMF and DMSO could be used as the proper solvents in crystallization of TKX-50. Correlation of TKX-50 solubility. To gain insight into the thermodynamics of TKX-50 dissolution reaction, the experimental mole fraction solubility data of TKX-50 was further correlated with a modified Apleblat equation12 as follows, and the results are shown in Figures 2 and 3. B ln x = A + + C ln(T ) (2) T where x is the mole fraction of solubility of TKX-50; T is the absolute temperature (list in Table 2); A, B, and C are the model parameters determined by the experimental solubility data.
ethanol
ethyl acetate
a
Standard uncertainties u are u(T) = 0.5 K, ur(p) = 0.05 and ur(x) = 0.05. (105)xcal and 100 δ are calculated by Apelbalt equation.
The relative deviation (δ) is defined in eq 3, and the related values are listed in Table 2. B
DOI: 10.1021/acs.jced.6b00009 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
Article
ranging from 293.15 to 323.15 K was measured by gravimetric method. The experimental results showed that TKX-50 has the highest solubility in DMSO and the lowest in ethyl acetate. The solubility of TKX-50 was increased when the temperature was increased in all of the investigated solvents, and the solubility in DMF showed the strongest dependency on temperature. Further, the experimental mole fraction solubility data of TKX50 was correlated with a simple Apleblat equation.
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AUTHOR INFORMATION
Corresponding Author
* Tel: +86-10-6891-8535. Fax: +86-10-6891-8535. E-mail:
[email protected]. Funding
We acknowledge the Excellent Young Scholar Research Fund of Beijing Institute of Technology of China (No. 3090012331542) and the Youth Innovation Fund of the North Chemical Industry Group (No. 3090041410054).
Figure 2. Temperature dependence of mole fraction solubilities (x) of TKX-50 in different solvents: ■, deionized water; ●, DMF; ▲, formic acid ▼, DMSO.
Notes
The authors declare no competing financial interest.
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Figure 3. Temperature dependence of mole fraction solubilities (x) of TKX-50 in different solvents: ★, toluene; ◀, ethanol; ▶, ethyl acetate.
δ=
(x − x calc) x
(3)
where x and xcalc are the experimental and calculated values, respectively. It can be seen from Table 3 that the Apleblat equation showed good correlation concerning the δ for each solution, which is calculated as less than 5%.
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CONCLUSIONS Solubility of TKX-50 in ethyl acetate, ethanol, deionized water, DMF, formic acid, toluene, and DMSO under the temperature Table 3. Parameters of Equation 3 for TKX-50 in Different Solvents solvent
A
B
C
R2
deionized water DMF formic acid toluene DMSO ethanol ethyl acetate
−125.61 −72.72 −81.10 −8.40 −26.63 −96.66 −84.41
3103.22 −1078.32 1651.42 −1318.95 −571.99 927.43 130.11
18.38 11.75 11.79 2.38 3.85 14.27 11.75
0.9967 0.9818 0.9853 0.9987 0.9936 0.9916 0.9905
REFERENCES
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DOI: 10.1021/acs.jced.6b00009 J. Chem. Eng. Data XXXX, XXX, XXX−XXX
