Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene

Article abstract of DOI:10.1007/s10973-020-09339-x

Two different single crystals of 1,3,5-trinitro-4,6-diazidobenzene (C₆HN₉O₆) were measured by X-ray single-crystal diffraction. The molecular weight of C₆HN₉O₆ is 295.16. Crystal I system i

Full text of DOI:10.1007/s10973-020-09339-x

Journal of Thermal Analysis and Calorimetry
https://doi.org/10.1007/s10973-020-09339-x
Crystal structure and thermal decomposition kinetics
of 1,3,5‑trinitro‑4,6‑diazidobenzene
Peilan Wang1 · Jingqi Wang2 · Jianlong Wang1
Received: 7 August 2019 / Accepted: 13 January 2020
© Akadémiai Kiadó, Budapest, Hungary 2020
Abstract
Two diferent single crystals of 1,3,5-trinitro-4,6-diazidobenzene (C6HN9O6) were measured by X-ray single-crystal difrac-
tion. The molecular weight of C6HN9O6 is 295.16. Crystal I system is orthorhombic, and space groups are Pbca, a=10.5199
(19) nm, b = 13.436 (3) nm, c = 15.235 (3) nm, β = 90°, V = 2153.4 (7) nm3, Z = 8, Dc = 1.821 g cm−3, μ = 0.164 mm−1,
F(000)=1184. Crystal II system is tetragonal, and space groups are P42/no a=b=19.412 (5) nm, c=5.9603 (17) nm, β=90°,
V=2246.0 (13) nm3, Z=8, Dc=1.746 g cm−3, μ=0.157 mm−1, F(000)=1184. Enthalpy of formation and detonation prop-
erties were calculated at the DFT-B3LYP/6-311++G ** level. It shows that these two compounds all have good detonation
performance, among which crystal I has higher detonation velocity (8.81 km s−1) and detonation pressure (34.65 GPa) than
those of crystal II. The thermal behavior of the crystal I was studied by diferential scanning calorimetry (DSC)–thermal
gravimetric (TG) analysis, melting peak is at 94.80 °C, and two decomposition exothermic peaks are at 126.39 °C and
212.10 °C, respectively, in DSC curve. According to the Kissinger and Flynn–Wall–Ozawa methods, the activation energy
(E) calculated for the frst decomposition of the crystal I is 109.25 kJ mol−1 and 110.67 kJ mol−1, respectively, and second
decomposition is 121.05 kJ mol−1 and 124.35 kJ mol−1, respectively. In addition, the accelerating rate calorimeter (ARC)
was used to further study the adiabatic decomposition behavior. The E of the two decompositions is 128.70 kJ mol−1 and
302.55 kJ mol−1, respectively, and the pre-exponential (A) is 1.02×1016 s−1 and 2.01×1035 s−1, respectively, by ARC data.
The mechanism functions were f(α)=2α0.5 (frst decomposition) and f(α)=3α2/3 (second decomposition).
Keywords 1,3,5-trinitro-4,6-diazidobenzene · Crystal structure · Detonation parameters · Thermal decomposition kinetics
Introduction
Therefore, it is suitable for using as conventional fuels, jet
fuels, and propellant additives. Organic azido is an important
active intermediate which can occur click reaction, cycload-
dition reaction, and Staudinger ligation [5, 6].
Compared with traditional explosives, such as TNT, RDX,
and HMX, nitrogen-rich compounds have excellent perfor-
mance including high nitrogen content, high enthalpy of
formation, safety, and environmentally friendly. They are
applied to high-energy sensitive explosives, rocket propel-
lants, gas-generating composition, and freworks composi-
tion, which broaden the applications of nitrogen-rich com-
pounds in energetic material feld [1–3]. Azide compounds
have a great density and a high burning rate, and per mole of
azide group is decomposed to release 314 kJ to 397 kJ [4].
Diferential scanning calorimetry (DSC), thermal gravi-
metric analysis (TG), and accelerating rate calorimeter
(ARC) are an efective way to study the thermal decompo-
sition process of a substance. Thermal decomposition kinetic
parameters, such as the apparent activation energy and pre-
exponential constant, are the main factors for determining
the thermal properties of energetic materials. Pourmortazavi
et al. [7] studied the thermal stability of NTO and KNF via
DSC, and they also studied the efect of nitro on the ther-
mal stability and decomposition kinetics of nitro-HTPB,
which revealed that the onset and maximum peak tempera-
tures increased due to the higher nitro content in HTPB and
increasing the DSC heating rate leads to the lower thermal
stability temperatures of the nitro-HTPB [8]. Pourmortazavi
et al. also studied the thermal behavior of energetic materials
* Jianlong Wang
wangjianlong@nuc.edu.cn
1
School of College of Chemical Engineering and Technology,
The North University of China, Taiyuan, China
2
Norinco Group Hubei DongFang Chemical Industry Co. Ltd,
Xiangyang, China
Vol.:(0123456789)
1 3

P. Wang et al.
when nanometer metal oxide is used as propellant [9, 10].
Li et al. researched the thermal properties of 3,5-dinitro-
1-oxygen-3,5-diazacyclohexane by DSC–TG technology.
The result shows that the 3,5-dinitro-1-oxygen-3,5-diaza-
cyclohexane is a low melting point compound with excellent
stability [11]. Zhang et al. [12] discussed the thermal prop-
erties of TNT and DNAN by ARC, which indicating that
DNAN has a relatively better thermal stability than TNT.
1,3,5-Trinitro-4,6-diazidobenzene (DATNB) is a high-
energy nitrogen-rich organic compound and an important
intermediate. 1,3,5-trinitro-4,6-diazidobenzene was origi-
nally made by British with 1,3,5-trinitro-4,6-dichloroben-
zene (DCTNB) and sodium azido in methanol and acetone
mixed system, the yield was 95%, and the melting point was
92–94 °C after refning [13]. Huo and Lv obtained DATNB
by reacting of DCTNB and sodium azide in dimethyl sulfox-
ide. The yield of DATNB was 90.9% [14, 15].
Preparation of DATNB crystals
1,3,5-Trinitro-4,6-diazidobenzene samples were syn-
thesized as proposed previously by Ref. 13. Chang-
ing the ratio of material and solvent, 2.82 g (0.01 mol)
of 1,3,5-trinitro-4,6-dichlorobenzene was placed in a
100-mL four-necked flask, 25.40 mL of acetone and
methanol was separately added, and a solution of sodium
azide (1.50 g) in water (5.4 mL) and methanol (5.4 mL)
was added dropwise. The reaction was carried out at room
temperature for 1 h. Then, the solution was poured into ice
water, and a solid was collected, washed, and dried. The
yield was 98.6%. The melting point is 92–94 °C. Anal.
FT-IR spectrum of DATNB is observed in Fig. 1. FT-IR
(KBr): 1552.92, 1338.92 (C–NO2), 3088.88 (Ar–H),
2160.77 (N≡N). Calcd. (%) for C6HN9O6: C, 24.41; H,
0.34; N, 42.71; O, 32.54. Found (%): C, 24.50; H, 0.36;
N, 43.28; O, 31.86. 1H NMR (Acetone-d6) δ: 8.937 (s,
1H Ar–H). 13C NMR (151 MHz, Acetone-d6) δ: 137.80,
133.38, 125.51, 125.22. EI-MS: m/z 296 (M−).
In this paper, the 1,3,5-trinitro-4,6-diazidobenzene
(DATNB) was synthesized from DCTNB. Its structure
was characterized by elemental analysis, Fourier-transform
infrared (FT-IR) spectroscopy, nuclear magnetic resonance
(NMR) spectroscopy, and mass spectrometry (MS) [16]. The
structure is further confrmed by X-ray single-crystal difrac-
tion. The detonation parameters of DATNB are an impor-
tant criterion for evaluating the performances of an energetic
material. Hence, we calculate the detonation velocity based
on the theoretical density of diferent crystal forms. To the
best of our information, there is no report about the thermal
decomposition kinetics of DATNB. This is the study of the
detonation parameters, thermal decomposition kinetics, and
decomposition mechanism functions of DATNB.
The azide group is easily afected by light. The produced
pale yellow solid turns red under the light [17]. The red solid
was dissolved in ethanol, and the bulk crystal I is obtained
by solvent evaporation at room temperature. The needle
crystal II was obtained by dissolving the pale yellow solid
in ethanol and evaporating with solvent at room temperature.
Crystal data and structure determination
Two crystals with diferent crystal forms were obtained
at room temperature by solvent evaporation. Crystal I
(0.22 mm × 0.15 mm × 0.08 mm) was a bulk crystal, and
crystal II (0.19 mm×0.08 mm×0.03 mm) was needle. The
two crystals were selected to determine their structure by
Bruker SMART APEX CCD 6000 area detector difrac-
tometer equipped with a graphite monochromator Mo K\α
radiation (λ=0.71073 Å). The two temperatures are 173 K
and 150 K, respectively. For I, a total of 1,2965 difraction
spots were collected in the range of 2.674° ≤ θ ≤ 26.409°
by w-scan scanning, of which 1740 [I>2σ(I)] were observ-
able difraction spots, and 2198 [Rint = 0.0191] difraction
points were for structure analysis and refnement. For II,
in the range of 1.484° ≤ θ ≤ 24.995°, a total of 1,5461 dif-
fraction points were collected by f and \w scans, including
1981 [I > 2σ(I)] observed ones and 1107 [Rint = 0.0191]
difraction points were for structural analysis and refne-
ment. All parameters were corrected by LP factors and
empirical absorption. The crystal structure was analyzed
using the SHELXL-97 program [18] and optimized using
the SHELXL-97 program [19]. The details of data collec-
tion and refnement are given in Table 1.
Experimental
General information
All regents used in experiments such as acetone, methanol,
dimethyl sulfoxide, ethyl acetate, and petroleum ether were
analytically pure and purchased from Institute of Chemi-
cal Reagents in Tianjin and used without further purif-
cation. Deionized water was self-made in the laboratory.
The elemental analysis was carried out on PE instrument
(Model CHNO-2000). 1H-NMR spectra were recorded on
a 300 MHz Bruker instrument with Acetone-d6 solvents.
The FT-IR spectra were measured on a VERTEX 80 pro-
duced by Bruker in Germany. MS spectra were carried on a
Q Exactive Mass Spectrometer produced by Thermo Fisher
Scientifc Company in Germany. Single-crystal X-ray dif-
fraction data were collected on an Agilent Xcalibur & Gem-
ini made by Agilent in America. Thermal analysis was car-
ried out on a METTLER DSC 3 and NETZSCH TG 209F1
Libra and ES-Accelerating Rate Calorimeter.
1 3

Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene
Fig. 1 FT-IR spectrum of the
prepared DATNB
BRUKER
3500
3000
2500
2000
1500
1000
500
Wavenumber cm–1
Table 1 Crystal data and
Item
Value
structure refnement for DATNB
Crystal I
Crystal II
Empirical formula
Formula mass
Temperature/K
Crystal system
Crystal size/mm3
Space group
a/nm
C6HN9O6
295.16
173
Orthorhombic
0.22×0.15×0.08
Pbca
10.5199 (19)
13.436 (3)
15.235 (3)
90
C6HN9O6
295.16
150
Tetragonal
0.19×0.08×0.03
P42/n
19.412 (5)
19.412 (5)
5.9603 (17)
90
b/nm
c/nm
β/°
V/nm3, Z
2153.4 (7), 8
1.821
0.164
2246.0 (13), 8
1.746
0.157
Dc/g cm−3
Μ/mm−1
F(000)
θ/°
h, k, and l range
Independent refection (Rint)
Goodness of ft on F2
R, wR (I>2σ(I))
1184
1184
1.484–24.995
−22–23, −23–23, −7–7
0.0191
1.056
0.0756, 0.1763
0.1418, 0.2025
0.264, −0.345
2.674–26.409
−13–13, −16–16, −16–19
0.0191
1.047
0.0435, 0.1243
0.0564, 0.1355
0.317, −0.260
R, wR (all data)
(Δρ)max, (Δρ)min/e nm−3
detonation velocities and pressures. The two diferent crys-
tal forms of DATNB have diferent theoretical densities.
The detonation performance can be refected by detonation
velocity and pressure. Enthalpy of formation and detonation
properties were calculated at the DFT-B3LYP/6-311++G**
level. The detonation velocities and detonation pressures
were predicted by the Kamlet formula [20].
Calculation of detonation velocity and pressure
The detonation parameters, density, and heat generation of
energetic compounds can predict the detonation performance
and safety of energetic compounds. Detonation velocity and
pressure are an important indicator of the performance of
energetic materials. The density directly determines the
1 3

P. Wang et al.
Thermal experimental instruments and conditions
Thermal analysis was performed using a DSC, TG, and ARC
instruments. DSC experiments are carried out with mg-scale
samples, and the heat evolved or consumed in the reaction is
estimated under isothermal conditions Therefore, the ther-
mal data obtained from DSC can be used as a baseline data
in determining safe operating temperatures because of the
non-adiabatic experimental conditions. The sample of crys-
tal I (~1 mg) was placed in a crucible and heated from 25
to 400 °C at the heating rates of 5, 10, 15, and 20 °C min−1
in a nitrogen atmosphere. Crystal I has the same thermal
decomposition behavior as crystal II, and there is no crystal
transformation.
ARC is a common apparatus to measure the thermal
behavior under adiabatic condition. Under adiabatic con-
ditions, the temperature and pressure in the reactor will
increase sharply and the samples may explode because the
heat generated from material decomposition is all used to
heat up the material itself. Therefore, it can supply more
safety to evaluate the materials under adiabatic condition
[21]. The specifc heat capacity was estimated by the law
of science as 1.50 J g−1 °C−1 [22]. The sample of crystal
I (0.198 g) was placed in a titanium alloy ball and heated
from 50 to 300 °C, the heating rate was 1.1 °C min−1, the
heating step was 5 °C, the waiting time was 15 min, and the
temperature rise rate sensitivity was 0.02 °C min−1.
Fig. 3 Molecular packing in crystal I
Results and discussion
Crystal structure description
The analysis of single crystal shows that this 1,3,5-trinitro-
4,6-diazidobenzene belongs to orthorhombic and tetragonal
crystal system with space group Pbca or P42/n with Z=8.
Due to the diferent crystal systems, the density of crystal
I is 1.821 g cm−3, and the crystal II is 1.746 g cm−3. The
molecular structures and packings are shown in Fig. 2–4.
Three parameters including bond lengths, bond angles, and
torsion angles are shown in Tables 2 and 3.
Fig. 4 Molecular packing in crystal II
As shown in Fig. 2, the two azide groups and the three
nitro groups are connected to C6, C4, C1, C3, and C5,
respectively. Figures 3 and 4 show that there are eight
ordered molecular structures of DATNB in a unit cell. The
bond lengths of N9–C3 and N2–C6 are 1.4644 (24)° and
1.3800 (25)°, respectively (listed in Table 2), which are
shorter than the average bond length of C–NO2 (1.468Å).
However, it found that the C5–N5 is 1.4730 (27) Å, which
is longer than 1.468Å, indicating that the nitro groups on C3
and C6 are more stable [23]. In addition, in Table 2, the bond
angles indicate that the structure of DATNB is symmetry.
Table 3 shows that the torsion angles of C1–C2–C3–C4,
C2–C3–C4–C4, C3–C4–C5–C6, and C4–C5–C6–C1 of
crystal I are 4.566 (276)°, − 7.017 (261)°, 3.713 (268)°,
and −6.406 (249)°, respectively, and those of the crystal II
are − 5.895 (700)°, 3.539 (600)°, 0.532 (623)°, and 0.088
O3
O4
N5
N2
N3
N4
N7
N6
C4
C3
C5
N8
C6
O5
O2
C1
N9
C2
H2
N1
O1
O6
Fig. 2 Molecular structure of the DATNB
1 3

Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene
Table 2 Bond lengths and bond angles of DATNB
Crystal I
Bond
Crystal II
Bond
Dist./Å
Bond
Dist./Å
Dist./Å
Bond
Dist./Å
O1–N1
O2–N1
C1–N1
N3–N4
N2–N3
N2–C6
O4–N5
O3–N5
C2–C1
C6–C5
C4–C3
1.2080 (23)
1.2136 (23)
1.4579 (23)
1.1088 (31)
1.2266 (26)
1.3800 (25)
1.2020 (29)
1.2064 (28)
1.3833 (25)
1.4032 (25)
1.4023 (26)
C5–N5
N7–N8
N7–N6
N6–C4
O5–N9
O6–N9
N9–C3
C2–C3
C1–C6
C5–C4
C2–H2
1.4730 (27)
1.1129 (25)
1.2598 (24)
1.3889 (25)
1.2236 (24)
1.2176 (23)
1.4644 (24)
1.3726 (25)
1.4099 (25)
1.3941 (26)
0.9501 (18)
O1–N1
O2–N1
C1–N1
N3–N4
N2–N3
N2–C6
O4–N5
O3–N5
C2–C1
C6–C5
C4–C3
1.2071 (69)
1.2258 (68)
1.4368 (61)
1.1096 (71)
1.2321 (60)
1.3765 (55)
1.2091 (54)
1.2094 (52)
1.3816 (70)
1.3783 (57)
1.3970 (58)
C5–N5
N7–N8
N7–N6
N6–C4
O5–N9
O6–N9
N9–C3
C2–C3
C1–C6
C5–C4
C2–H2
1.4756 (56)
1.1212 (69)
1.2562 (55)
1.3817 (58)
1.2121 (60)
1.2257 (66)
1.4788 (55)
1.3642 (65)
1.4112 (56)
1.4008 (55)
0.9506 (51)
Angle
°
Angle
°
Angle
°
Angle
°
C1–C6–C5
C2–C1–C6
N1–C1–C2
N1–C1–C6
N2–C6–C1
N2–C6–C5
114.876 (159)
120.958 (162)
115.349 (147)
123.662 (155)
133.837 (170)
111.287 (155)
C3–C4–C5
C2–C3–C4
N9–C3–C2
N9–C3–C4
N6–C4–C3
N6–C4–C5
115.805 (169)
120.770 (166)
116.522 (157)
122.363 (163)
130.775 (173)
113.415 (156)
C1–C6–C5
C2–C1–C6
N1–C1–C2
N1–C1–C6
N2–C6–C1
N2–C6–C5
114.777 (366)
119.839 (386)
227.366 (401)
122.661 (374)
132.346 (372)
112.83 (358)
C3–C4–C5
C2–C3–C4
N9–C3–C2
N9–C3–C4
N6–C4–C3
N6–C4–C5
114.995 (352)
120.155 (403)
117.740 (402)
121.998 (352)
131.43 (39)
113.572 (359)
Table 3 Torsion angles of DATNB
Crystal I
Crystal II
Torsion angle
°
Torsion angle
°
Torsion angle
°
Torsion angle
°
O1–N1–C1–C2
O4–N5–C5–C6
O5–N9–C3–C4
C2–C3–C4–C5
C4–C5–C6–C1
13.840 (241) N3–N4–C6–C1
75.057 (254) N7–N6–C4–C3
−27.544 (260) C1–C2–C3–C4
−7.017 (261) C3–C4–C5–C6
−6.406 (249)
−4.856 (361) O1–N1–C1–C2
−13.959 (322) O4–N5–C5–C4
4.566 (276) O5–N9–C3–C2
3.713 (268) C2–C3–C4–C5
C4–C5–C6–C1
−26.200 (673) N3–N4–C6–C1
−81.798 (485) N7–N6–C4–C3
24.614 (609) C1–C2–C3–C4
3.539 (600) C3–C4–C5–C6
0.088 (582)
−18.501 (762)
21.667 (703)
−5.895 (700)
0.532 (623)
(582)°, respectively. The data show that the coplanarity of
the six atoms of the benzene ring is strong. Furthermore,
the torsion angles of O1–N1–C1–C2, N3–N4–C6–C1,
O4–N5–C5–C6, N7–N6–C4–C3, and O5–N9–C3–C4 of
crystal I are 13.840 (241)°, −4.856 (361)°, 75.057 (254)°,
−13.959 (322)°, and −27.544 (260)°, respectively. For crys-
tal II, the torsion angles of O1–N1–C1–C2, N3–N4–C6–C1,
O4–N5–C5–C6, N7–N6–C4–C3, and O5–N9–C3–C4 are
−26.200 (673)°, −18.501 (762)°, −81.798 (485)°, 21.667
(703)°, and 24.614 (609)°, respectively. The data indicate
that the fve groups are not in the same plane with the ben-
zene ring. However, compared with crystal I, dihedral angles
of crystal II between the groups attached to C1, C4, C5, C6
of the benzene ring are larger. Due to the infuence of space
steric, the dihedral angle of nitro group has changed. In addi-
tion, there is a strong π–π stacking in the molecule, and the
intramolecular and intermolecular hydrogen bonds are weak.
1 3

P. Wang et al.
Table 4 Properties of DATNB,
Compound
M/g mol−1
ρ/g cm−3
Q/kcal g−1
D/km s−1
P/GPa
RDX, and HMX
Crystal I (DATNB)
Crystal II (DATNB)
RDX
292
292
222
296
1.821
1.746
1.78
1.80
1.80
1.25
1.25
8.81
8.61
8.86
9.10
34.65
32.49
34.23
34.40
HMX
1.90
12
10
8
105
100
95
90
85
80
75
70
65
60
55
50
20
15
10
212.10
221.44 °C
TG
DSC
5 °C min–1
10 °C min–1
15 °C min–1
20 °C min–1
216.48 °C
212.10 °C
6
126.39
4
2
134.41 °C
131.08 °C
126.39 °C
0
201.21 °C
5
0
– 2
– 4
119.42 °C
94.80
– 6
50 100 150 200 250 300 350 400
– 5
Temperature/°C
50
100
150
200
250
300
350
400
Temperature/°C
Fig. 5 DSC–TG curves of DATNB
Fig. 6 Efect of DSC heating rate on decomposition temperature of
investigated energetic samples
Calculation results of detonation parameters
Table 5 First decomposition kinetics basic data of DSC
For comparison, detonation parameters of DATNB, RDX,
and HMX are calculated simultaneously. The results are
shown in Table 4.
β/K min−1 TP/K
103TP−1/K−1 Kissinger method FWO method
In (β/T2P)/min−1
lg β/K min−1
K−1
Table 4 shows that the detonation velocity and pressure
of the crystal I (DATNB) are greater than those of the crys-
tal II (DATNB), which indicates that crystal I has better
detonation performance. The detonation heat and detonation
pressure of DATNB are greater than RDX and HMX, but the
detonation velocity is less than RDX and HMX, indicating
that DATNB is an energetic compound with a high detona-
tion heat and a high detonation pressure.
5
392.57 2.55
−10.34
−9.68
−9.30
−9.02
0.70
1.00
1.18
1.31
10
15
20
399.54 2.50
404.17 2.47
407.56 2.45
Thus, it can be seen that the azide group can increase the
detonation pressure, because azide group can release a large
amount of nitrogen gas when the explosion occurs.
Table 6 Second decomposition kinetics basic data of DSC
β/K min−1 TP/K
103TP−1/K−1 Kissinger method FWO method
In (β/T2P)/min−1
lg β/K min−1
K−1
Thermal behavior of DATNB
5
474.36 2.11
−10.71
−10.07
−9.68
−9.41
0.70
1.00
1.18
1.31
The thermal analysis of DSC–TG results
10
15
20
485.25 2.06
489.63 2.04
494.59 2.02
The typical DSC–TG curves (Fig. 5) indicate that the ther-
mal behaviors of title compound can be described in three
stages which contain an endothermic and two exothermic
processes.
the frst mass loss is 12% and the second mass loss is 23%,
which is consistent with the two exothermic stages on the
DSC curve. In addition, the decomposition starts after melt-
ing, and the ∆Hd of the two processes are 899.38 J g−1 and
It shows that the melting endothermic peak of the com-
pound is 94.80 °C, followed by two exothermic decompo-
sition peaks at 126.39 °C and 212.10 °C, respectively. In
the TG curve, there are two stages of mass loss, of which
1 3

Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene
– 9.0
– 9.2
– 9.4
– 9.6
– 9.4
– 9.6
– 9.8
– 10.0
– 10.2
– 10.4
– 10.6
– 10.8
– 9.8
β
– 10.0
β
– 10.2
– 10.4
2.00
2.02
2.04
2.06
2.08
2.10
2.12
2.44
2.46
2.48
2.50
2.52
2.54
2.56
103Tp–1/K–1
103Tp–1/K–1
Fig. 9 ln(β/T2P) versus T−P1 by Kissinger method for second decompo-
Fig. 7 ln(β/T2P) versus T−P1 by Kissinger method for frst decomposi-
sition
tion
1.4
1.3
1.2
1.1
1.0
1.4
1.3
1.2
1.1
1.0
β
0.9
0.9
β
0.8
0.7
0.6
0.8
0.7
0.6
2.44
2.46
2.48
2.50
2.52
2.54
2.56
2.00
2.02
2.04
2.06
2.08
2.10
2.12
103Tp–1/K–1
103Tp–1/K–1
Fig. 8 lnβ versus T−P1 by FWO method for frst decomposition
Fig. 10 lnβ versus T−P1 by FWO method for second decomposition
(
)
1835.25 J g−1, respectively. Figure 4 shows that the onset
temperature of the second decomposition is very close to
the end temperature of the frst decomposition. So, we can
conclude that of the title compound is easy to lead to ferce
secondary decomposition during the decomposition process.
Figure 6 presents DSC curves for decomposition of the
studied energetic samples at diferent heating rates. As seen
in this fgure, decomposition peaks of the samples were
shifted to the higher temperatures by increasing the heating
rate. The data of β and TP at two decomposition stages are
shown in Tables 5 and 6.
(
)
ꢀ
AR
E
E
ln
= ln
−
(1)
(2)
TP2
RTP
[
]
AE
0.4567E
log ꢀ = log
− 2.315 −
RG(ꢁ)
RTP
where β is the linear heating rate (K min−1), TP is the peak
temperature of the DSC curves (K), A is the pre-exponential
constant (s−1), R is the gas constant (J mol−1 K−1), E is the
apparent activation energy (kJ mol−1), and G (α) is the inte-
gral form of reaction mechanism function.
Kissinger and Flynn–Wall–Ozawa methods which are
two integral methods [24–26] are used to calculate the
kinetic parameters (the apparent activation energy (E) and
pre-exponential constant (A)) of the title compound.
Kissinger Eq. (1) and Flynn–Wall–Ozawa Eq. (2) are
described as follows:
Figures 7 and 8 are ftted from the data in Table 5. Fig-
ure 7 shows a ftting curve correlated by Kissinger equation,
which illustrates the relationship between ln(β/T2P) and TP−1.
The slope and intercept of the line are −13.14 and 23.16,
1 3

P. Wang et al.
Table 7 Kinetics parameters of
Ek/kJ mol−1
A/s−1
rk2
Eo/kJ mol−1
ro2
title compound
First decomposition
second decomposition
109.25
121.05
2.50×1015
2.38×1012
0.9998
0.9937
110.67
124.35
0.9998
0.9940
35
and intercept of the Flynn–Wall–Ozawa method, respec-
tively, with a correlation coefcient (r2) of 0.9940. Finally,
the Eo2 of second decomposition stage is 124.35 kJ mol−1.
The kinetic parameters values (E and A) determined
by the Kissinger and the Flynn–Wall–Ozawa method
are shown in Table 7. We can see that the E obtained by
Kissinger method agrees well with these obtained by the
Flynn–Wall–Ozawa method, and the correlation coefcient
(r2) is close to 1, indicating the satisfactory validity of the
results. The lower apparent activation (Table 7) of title com-
pound indicates that less energy is required in its thermal
decomposition, so it exists unstably. Therefore, the tempera-
ture of synthesis and storage of the compound are worthy
of attention.
Pressure/bar
Temp/°C
250
200
150
100
50
30
25
20
15
10
5
0
0
– 5
– 50
– 100 0 100 200 300 400 500 600 700 800 900
Time/min
Fig. 11 Temperature and pressure versus time
respectively, and the correlation coefcient (r2) is 0.9998.
Therefore, the frst decomposition activation energy Ek1
and pre-exponential constant A calculated by the Kissinger
method are 109.25 kJ mol−1 and 8.33 × 1016 s−1, respec-
tively. Using Flynn–Wall–Ozawa method, the relationship
between lgβ and T−P1 is graphically illustrated in Fig. 8.
The slope and intercept of the line we obtained from the
Flynn–Wall–Ozawa equation are −6.07 and 16.19, respec-
tively, with a correlation coefcient of 0.9998. So, activa-
tion energy Eo1 of the frst decomposition obtained by the
Flynn–Wall–Ozawa method is 110.67 kJ mol−1.
The thermal analysis of ARC results
The adiabatic decomposition parameters of title compound
have been studied by ARC. Figures 11 and 12 show the
results of the test.
As shown in Figs. 11 and 12, after fve H–W–S periods, the
frst self-decomposition reaction of DATNB starts at 80.6 °C.
(The temperature rise rate is 0.08 °C min−1.) The temperature
rise rate reaches a maximum of 1.05 °C min−1 after 49.5 min,
and the temperature and pressure are 101.31 °C and 4.83 bar,
respectively. After that, the self-heating rate decreases due to
the consumption of reactants. The frst stage of heat release
ends at 103.91 °C. The second exotherm starts at 135.67 °C
(the temperature rise rate is 0.08 °C min−1) after several
H–W–S modes. The temperature rise rate is 4158.6 °C min−1
when the temperature is 214.88 °C, after 232.43 min. The
pressure rise rate is not detected because it is too large. The
reason may be that DATNB decomposes rapidly and produces
Figures 9 and 10 are ftted from the data in Table 6.
The slope and intercept of the line in Fig. 9 are − 14.56
and 20.00, respectively, and the correlation coefcient is
0.9937. Thus, Ek2 and A of the second-order decomposition
acquired using the Kissinger method are 121.05 kJ mol−1
and 2.38×1012 s−1. In Fig. 10, −6.82 and 15.08 are the slope
Fig. 12 Decomposition tem-
perature rate verse temperature;
a frst decomposition b second
decomposition
(a)1.2
(b)
4000
1.0
0.8
3000
2000
1000
0
0.6
0.4
0.2
0.0
– 1000
– 0.2
78 81 84 87 90 93 96 99 102 105
Temp/°C
120 140 160 180 200 220 240 260
Temp/°C
1 3

Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene
Table 8 Self-heating decomposition parameters of DATNB by ARC
Table 8 shows that the thermal decomposition tem-
perature of DATNB is lower and the released energy is
higher. The time of the start of thermal decomposition
and the maximum thermal decomposition rate is 4.12
and 19.34 min, respectively. It is proved that there is
no strong autocatalytic phenomenon in its thermal
decomposition.
Parameters
First stage
Second stage
Values Corr. Values Corr.
Onset temperature/°C
80.60 –
0.08 0.97
135.67 –
0.03 0.36
Onset temperature
rate/°C min−1
Max self-heating
1.05 12.62 4158.62 49,986.61
In addition, in real situations, energetic materials may
sufer the adiabatic decomposition: ammunition with big
size and low heat conductivity, energetic materials heated
up by forced heating and showing a temperature increase
in their center by heat accumulation (as in slow cook-of).
In comparison with DSC, ARC can determine the self-
heating of samples in an adiabatic environment. In this
way, the decomposition process is controlled by sample
rather than forced from an outside temperature program,
which is similar to the real adiabatic decomposition. ARC
determines the self-heating decomposition of the sample
in an adiabatic environment with large sample amounts.
Therefore, the ARC measurements were implemented to
research the adiabatic thermal decomposition mechanism
functions of DATNB. Activation energy (E) and pre-expo-
nential factor (A) of the sample are calculated under adi-
abatic conditions by rate constant method and mechanism
functions method. For an nth-order reaction with a single
reaction, the self-heat rate (SHR) of adiabatic system can
be expressed as follows [29]:
rate/°C min−1
Temperature at max rate/°C
Final temperature/°C
Adiabatic temperature rise/°C
Time to maximum rate/min
Onset pressure/bar
101.31 –
103.91 360.79 251.66 1650.19
23.31 280.19 126.00 1514.52
49.50 4.12
1.52 –
4.83
214.88 –
232.43 19.34
6.21 –
10.54 –
Pressure at max rate/bar
large amounts of gas products. It should be note that the high
temperature rise rate and pressure rise rate indicate that the
released energy may be generated and then explode if the
decomposition of DATNB occurs uncontrolled in a confned
space.
During the exothermal decomposition, the measuring ves-
sel is also hated up. This means that the self-heating rate is
decreased by the measuring vessel compared to measurement
without measuring vessel. Therefore, it is necessary to correct
the tested parameters. The corrected and measured self-heating
decomposition parameters of DATNB are given in Table 8.
The formulas of the inertia factor ϕ and the corrected charac-
teristic parameters are defned as follows [27, 28]:
mT
k∗ = kC0n−1
=
[
]
n
Tf−T
ΔTad
(8)
ΔTad
Mb × Cvb
where k* is the pseudozero-order rate constant at the tem-
perature T, C0 is the initial concentration of the reactant, T
is the temperature at time t, mT is the temperature rate at the
temperature T, ∆T is the adiabatic temperature rise, and n
is the reaction order.
� = 1 +
(3)
MS × Cvs
ΔTs = �ΔT
(4)
Arrhenius equation:
m0s = �m0
(5)
−E
∗
(9)
RT
k = Ae
Tfs = T0 + �ΔT
(6)
where A is the apparent pre-exponential factor, and E is
apparent activation energy.
ꢀ
ꢀs =
.
By substituting and rearranging Eq. (9) into Eq. (8), We
can get the following:
mT
(7)
�
where Mb is the mass of the bomb, Cvb is the specifc heat of
bomb, Ms is the mass of the sample, and Cvs is the specifc
heat of reaction sample. ∆T is the adiabatic temperature rise,
m0 is the initial self-heating rate, T0 is the initial decom-
position temperature, θ is the time to maximum rate, and
subscript s is the corrected value.
E
ln k∗ = ln
= ln A −
[
]
n
Tf−T
ΔT
RT
(10)
ΔT
According to Eq. (10), the curves of Ink* versus T−1 for the
self-heating decomposition of DATNB are illustrated in
1 3

P. Wang et al.
Fig. 13 ln k* versus T−1 of
DATNB a frst decomposition;
b second decomposition
(a)
(b)
0
1
0
n = 0
n = 0.5
n = 1
n = 2
n = 0
n = 0.5
n = 1
– 1
– 2
– 3
– 1
– 2
– 3
– 4
– 5
– 4
– 5
– 6
– 7
– 6
– 7
– 8
– 8
2.24 2.28
2.32
2.36 2.40
2.44
2.48
2.64 2.67 2.70 2.73 2.76 2.79 2.82 2.85
1000T–1/k–1
1000T–1/k–1
Table 9 Adiabatic kinetics parameters of frst decomposition of
Fig. 13. The activation energy and the pre-exponential fac-
tor are calculated from the linear relationship of ln k*–T−1,
and they are listed in Tables 9 and 10.
DATNB
n
Ea/kJ mol−1
A/s−1
r2
The apparent activation energy and pre-exponential fac-
tor of adiabatic decomposition process are also calculated
by using mechanism functions method that comes from
Achar–Brindley–Sharp method. After taking logarithm,
formula 11 is deformed as follows:
0
0.5
1
128.70
201.53
274.45
1.02×1016
4.49×1026
2.00×1037
0.9987
0.9612
0.9147
[
]
mT
E
Table 10 Adiabatic kinetics parameters of second decomposition of
ln
= ln(AΔTad) −
(11)
f(ꢀ)
RT
DATNB
n
Ea/kJ mol−1
A/s−1
r2
where T is the temperature; mT = dT/dt is the temperature
rate; ∆Tad is the adiabatic temperature rise; and f(α) symbol-
izes the kinetic model in the form of diferential equation. α
0
0.5
1
218.16
239.28
260.39
302.55
3.89×1024
1.84×1027
8.80×1029
2.01×1035
0.9632
0.9707
0.9762
0.9832
s y m b o l i z e s
t h e
r e a c t i o n
d e g r e e ,
ꢀ = (c0 − c)∕c0 = (T − T0)∕ΔTad; then, the data are substi-
tuted into 16 kinds of thermal decomposition mechanism
2
[
]
mT
functions (Table 11), respectively [30, 31]. ln
T
versus
f(ꢀ)
−1 should give a straight line with a slop −E/R proving the
Table 11 16 types of thermal decomposition mechanism functions
kinetic model which is correctly chosen. The results are
shown in Figs. 14 and 15. The liner ftting results are listed
in Tables 12 and 13.
Item
f(α)
1
2
3
4
5
6
7
8
1/(2α)
Table 12 indicates that, for the frst decomposition, the
highest correlation coefcient and the corresponding kinetic
model are model 2. Table 13 indicates that, for the second
decomposition, the highest correlation coefcient and the
corresponding kinetic model are model 11.
2α0.5
1−α
(1−α)2
2(1−α)3/2
[−In(1−α)]−1
1.5(1−α)2/3[1−(1−α)1/3 −1
1.5(1+α)2/3[(1+α)1/3 −1]−1
1.5(1−α)[−In(1−α)]1/3
4(1−α)[−In(1−α)]3/4
3α2/3
]
9
10
11
12
13
14
15
16
3(1−α)2/3
2(1−α)1/2
3(1−α)[−In(1−α)]2/3
2(1−α)[1−In(1−α)]1/2
(2/3)[(1−α)−1/3 −1]−1
1 3

Crystal structure and thermal decomposition kinetics of 1,3,5-trinitro-4,6-diazidobenzene
4
Fig. 14 ln((mT)/(f(α))) versus
2
(a)
(b)
model 1
model 2
model 3
model 4
model 5
model 6
model 7
model 8
model 9
T
−1 of DATNB frst decomposi-
model 10
model 11
model 12
model 13
model 14
model 15
model 16
1
0
2
0
tion
– 1
– 2
– 3
– 4
– 5
– 6
α
α
– 2
– 4
– 6
– 8
– 7
2.64
2.64
2.68
2.72
1000 T–1/K–1
2.76
2.80
2.84 2.88
2.68
2.72
2.76
2.80
2.84 2.88
1000 T–1/K–1
Fig. 15 ln((mT)/(f(α))) versus
2
1
6
4
(a)
(b)
model 9
model 1
model 2
model 3
model 4
model 5
model 6
model 7
model 8
T
−1 of DATNB second decom-
model 10
model 11
model 12
model 13
model 14
model 15
model 16
position
0
2
α
α
– 1
– 2
– 3
– 4
– 5
0
– 2
– 4
– 6
– 8
2.24 2.28 2.32 2.36 2.40 2.44 2.48 2.52
2.24 2.28 2.32 2.36 2.40 2.44 2.48 2.52
1000 T–1/K–1
1000 T–1/K–1
Table 12 Kinetic parameter regression results for the frst decomposi-
Table 13 Kinetic parameter regression results for the second decom-
tion
position
Item
r2
ln(A∆Tad)
−E/R
2.95
−24.62
−0.27
14.88
7.30
9.09
16.83
−4.40
−8.45
−18.66
−27.68
−5.33
−7.85
−16.62
−4.17
11.78
E/kJ mol−1
A/s−1
Item
r2
ln(A∆Tad)
−E/R
E/kJ mol−1
A/s−1
1
2
3
4
5
6
7
8
0.0642
0.9588
0.0027
0.6397
0.4400
0.4387
0.7660
0.1462
0.5720
0.7502
0.9413
0.7156
0.9157
0.7328
0.4377
0.5894
−10.75
64.84
–
–
1
2
3
4
5
6
7
8
0.9334
0.9697
0.7288
0.0378
0.1975
0.8972
0.6438
0.9532
0.8283
0.8970
0.9719
0.8837
0.9204
0.8863
0.8223
0.8464
49.37
66.75
28.64
−3.90
11.67
36.82
18.52
55.02
36.36
45.53
68.43
38.39
44.22
43.79
34.29
30.18
−21.34
−29.06
−12.03
2.44
−4.80
−16.04
−8.58
−25.09
−15.51
−19.87
−29.92
−16.85
−19.26
−18.99
−14.90
−13.40
177.42
241.60
100.02
–
39.91
133.36
71.33
208.60
128.95
165.20
248.75
140.09
160.13
157.88
123.88
111.41
5.07×1019
1.79×1027
5.04×1010
–
204.69
2.24
–
–
–
6.19×1026
−0.66
−41.20
−21.84
−27.84
−0.07
6.45
21.51
48.74
72.99
11.75
18.91
43.38
8.87
−35.74
–
–
–
–
2.15×103
1.80×1014
2.03×106
1.44×1022
1.14×1014
1.09×1018
9.62×1027
8.65×1014
2.94×1017
1.91×1017
1.43×1013
2.35×1011
–
–
36.58
70.25
155.14
230.13
44.31
65.26
138.18
34.67
–
27.15
9
9.42×107
6.31×1019
2.15×1030
5.44×103
6.99×106
2.97×1017
3.05×102
–
9
10
11
12
13
14
15
16
10
11
12
13
14
15
16
1 3

P. Wang et al.
4,4′,6,6′-tetraazidoazo-1,3,5-triazine (TAAT). Chin J Org Chem.
2012;31:1484–9.
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In this study, the synthesis and characterization of the
energetic material 1,3,5-trinitro-2,4-diazidobenzene and
its crystal structure, detonation parameters, and thermal
properties are studied.
6. Li YC, Zhang XJ, Fu W, Pang SP, Zhao CL. Synthesis, char-
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1. Crystal I belongs to orthorhombic with the space
group of Pbca, a=10.5199 (19) nm, b=13.436 (3) nm,
c=115.235 (3) nm, β=90°, V=2153.4 (7) nm3, Z=8,
Dc = 1.821 g cm−3, μ = 0.164 mm−1, F(000) = 1184.
Crystal II belongs to tetragonal with the space groups
of P42/no. a = b = 19.412 (5) nm, c = 5.9603 (17) nm,
β=90°, V=2246.0 (13) nm3, Z=8, Dc=1.746 g cm−3,
μ=0.157 mm−1, F(000)=1184.
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2. The detonation velocity and the detonation pressure of
crystal I are 8.81 km s−1 and 34.65 GPa, respectively,
and those of crystal II are 8.61 km s−1 and 32.49 GPa,
respectively. The detonation velocity of crystal I is lower
than that of RDX and HMX, but the detonation pressure
is higher than that of HMX and RDX.
10. Mirzajani V, Farhadi K, Pourmortazavi SM. Catalytic efect of
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Chim Sin. 2015;31:2049–56.
3. The non-isothermal decomposition kinetic and ther-
modynamic parameters are obtained. The activation
energy shows good correction by the Kissinger and
Flynn–Wall–Ozawa methods, and the values obtained
by Flynn–Wall–Ozawa method are nearly close to those
obtained by Kissinger method.
12. Zhang CY, Jin SH, Ji JW, Jing BC, Bao F, Zhang GY, Shu QH.
Thermal hazard assessment of TNT and DNAN under adiabatic
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4. The adiabatic decomposition experiment by ARC
reveals that the maximum self-heating rate of DATNB is
4158.62 °C min−1 at second decomposition. After a long
induction period, the reaction will become uncontrol-
lable, which may result in an explosion accident fnally.
The apparent activated energy calculated under adiabatic
condition is 128.70 kJ mol−1 (n=0) and 302.55 kJ mol−1
(n=2), respectively.
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5. Under adiabatic condition, the mechanism functions for
decomposition of DATNB are f(α)=2α0.5 (frst decom-
position) and f(α)=3α2/3 (second decomposition).
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Acknowledgements We thank the Center of Testing and Analysis,
Shanghai Institute, for support.
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