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Thermogravimetric analysis, kinetic study, and pyrolysis–GC/MS analysis of 1,1ʹ-azobis-1,2,3-triazole and 4,4ʹ-azobis-1,2,4-triazole
© The Author(s) 2018
Received: 12 September 2017
Accepted: 26 January 2018
Published: 1 March 2018
In general, the greater the number of directly linked nitrogen atoms in a molecule, the better its energetic performance, while the stability will be accordingly lower. But 1,1ʹ-azobis-1,2,3-triazole (1) and 4,4ʹ-azobis-1,2,4-triazole (2) show remarkable properties, such as high enthalpies of formation, high melting points, and relatively high stabilities. In order to rationalize this unexpected behavior of the two compounds, it is necessary to study their thermal decompositions and pyrolyses. Although a great deal of research has been focused on the synthesis and characterization of energetic materials with 1 and 2 as the backbone, a complete report on their fundamental thermodynamic parameters and thermal decomposition properties has not been published.
Thermogravimetric–differential scanning calorimetry were used to obtain the thermal decomposition data of the title compounds. Kissinger and Ozawa–Doyle methods, the two selected non-isothermal methods, are presented for analysis of the solid-state kinetic data. Pyrolysis–gas chromatography/mass spectrometry was used to study the pyrolysis process of the title compounds.
The DSC curves show that the thermal decompositions of 1 and 2 are at different heating rates involved a single exothermic process. The TG curves provide insight into the total weight losses from the compounds associated with this process. At different pyrolysis temperatures, the compositions and types of the pyrolysis products differ greatly and the pyrolysis reaction at 500 °C is more thorough than 400 °C.
Apparent activation energies (E) and pre-exponential factors (lnA/s−1) are 291.4 kJ mol−1 and 75.53 for 1; 396.2 kJ mol−1 and 80.98 for 2 (Kissinger). The values of E are 284.5 kJ mol−1 for 1 and 386.1 kJ mol−1 for 2 (Ozawa–Doyle). The critical temperature of thermal explosion (T b ) is evaluated as 187.01 °C for 1 and 282.78 °C for 2. The title compounds were broken into small fragment ions under the pyrolysis conditions, which then might undergo a multitude of collisions and numerous other reactions, resulting in the formation of C2N2 (m/z 52), etc., before being analyzed by the GC/MS system.
Triazoles are a class of typical nitrogen-rich compounds, which have been widely used in novel energetic materials, medicine, catalysis, and other fields [1–4]. Over several decades, many studies have shown that azobis-triazole compounds have good energetic properties. This is due to their structure with multiple nitrogen atoms linked directly, along with many C–N and N–N single or double bonds in the molecule, which have good energetic properties [5–11]. Indeed, compared with a single triazole ring, energetic properties such as energy density, heat of formation, detonation velocity, and detonation pressure, can be significantly improved [8, 12–16].
In general, the greater the number of directly linked nitrogen atoms in a molecule, the better its energetic performance, but stability will be accordingly lower [5, 12, 13, 17–22]. The title compounds 1,1ʹ-azobis-1,2,3-triazole (1) and 4,4ʹ-azobis-1,2,4-triazole (2) show remarkable properties, such as high enthalpies of formation, high melting points, and relatively high stabilities [5, 13, 14, 17]. In order to rationalize this unexpected behavior of the two compounds, it is necessary to study their thermal decompositions and pyrolyses. Although a great deal of research has been focused on the synthesis and characterization of energetic materials with 1 and 2 as the backbone [5, 13, 17, 19], a complete report on their fundamental thermodynamic parameters and thermal decomposition properties has not been published.
The stability of the title compounds can be quantitatively determined by studying their thermodynamic properties, such as apparent activation energy (E) and pre-exponential factor (A) of thermal decomposition, and the critical temperature of thermal explosion (T b ).
Common methods for studying non-isothermal solid-state kinetics
Thermal pyrolysis refers to chemical decomposition caused by heat, when the thermal energy applied to the sample exceeding the chemical bond energy of the molecules. PY–GC/MS has been widely used to investigate decomposition processes and pyrolysis products . Analytical pyrolysis allows the thermal breakdown of a molecule into smaller fragments, which are then selected and analyzed by the GC/MS system, providing insight into the decomposition of the sample. The PY–GC/MS can study the thermal pyrolysis of an energetic material and provides information about the nature of the explosion reaction products by GC/MS analysis, which give the information about the reaction process. These in turn can be used to evaluate whether the used explosives are environmental friendly from the identification of the explosive residue species. In addition, the identification of the explosive residue species can also be used in military and counterterrorism practice.
Compound 1 and 2 can be prepared by oxidation of the N–NH2 moieties in 1-amino-1,2,3-triazole and 4-amino-1,2,4-triazole, respectively, with sodium dichloroisocyanurate (SDIC). In this study, the thermal decomposition processes of 1 and 2 have been investigated by dynamic TG–DSC under nitrogen atmosphere at different heating rates, and by PY–GC/MS under helium atmosphere at set temperatures of 400 and 500 °C, respectively. Kinetic parameters have been obtained by two model-free methods, the Kissinger method and the Ozawa–Doyle method combined with a kinetic compensation effect. The data reported herein are expected to be of broad interest to researchers engaged in the study and applications of 1 and 2.
Materials and methodology
Synthesis of 1,1ʹ-azobis-1,2,3-triazole (1) 
1-Amino-1,2,3-triazole (1.26 g, 15 mmol) was dissolved in CH3CN (40 mL). The solution was cooled to – 5 to 0 °C and a solution of SDIC (3.33 g, 15 mmol) in water (10 mL) and CH3COOH (5 mL) was added dropwise. The reaction mixture was further stirred at 0 °C for 30 min. It was then neutralized with NaHCO3 and filtered. The filtrate was concentrated to afford the product, which was obtained as a slightly yellow solid after recrystallization from acetone. 1H NMR (400 MHz, [D6]DMSO, 25 °C, TMS): δ = 9.17 (2H, d), 8.21 ppm (2H, d); 13C NMR (100 MHz, [D6]DMSO, 25 °C, TMS): δ = 134.8, 118.0 ppm; IR (KBr): ν = 3128, 1625, 1482, 1320, 1225, 1171 cm−1; MS: m/z 165.0 [M + H]+; elemental analysis calcd. (%) for C4H4N8 (164): C, 29.27; H, 2.44; N, 68.29; found: C, 29.45; H, 2.32; N, 68.23.
Synthesis of 4,4ʹ-azobis-1,2,4-triazole (2) 
Acetic acid (5 mL) was added to a solution of SDIC (5.09 g, 23 mmol) in water (40 mL) with vigorous stirring at 30 °C. After 1 h, the mixture was cooled to 5 °C and a solution of 4-amino-1,2,4-triazole (2.07 g, 25 mmol) in water (10 mL) was added. The reaction mixture was vigorously stirred at 15 °C for 1 h. It was then cooled, and the precipitate that formed was collected by filtration and washed with water at 60 °C. After drying in vacuo, a white product was obtained. 1H NMR (400 MHz; D2O, 25 °C, TMS): δ = 7.22 ppm (4H, s); 13C NMR (100 MHz; D2O, 25 °C, TMS): δ = 138.57 ppm; IR (KBr): ν = 3114, 1493, 1368, 1317, 1180 cm−1; MS: m/z 164 (M+); elemental analysis calcd. (%) for C4H4N8 (164): C, 29.27; H, 2.44; N, 68.29; found: C, 29.32; H, 2.48; N, 68.2.
The thermal decompositions of 1 and 2 under flowing N2 were investigated using a thermogravimetric analyzer (Netzsch STA 449 C; Selb, Germany) and a differential scanning calorimeter (DSC Q2000; New Castle, USA). The TG conditions were as follows: sample mass, ca. 1.0 mg; heating rates, 5, 7, 10, 13, and 20 °C min−1 for 1, and 5, 7, 10, 15, and 20 °C min−1 for 2; atmosphere, N2 (flow rate 30 mL min−1); temperature range, 20–400 °C. The DSC conditions were as follows: heating rates, 5, 7, 10, 13, and 20 °C min−1 for 1, and 5, 7, 10, 15, and 20 °C min−1 for 2; atmosphere, N2 (flow rate 30 mL min−1); temperature range, 20–400 °C. All TG–DSC data were analyzed using Proteus Analysis software.
Thermal pyrolyses of 1 and 2 were investigated using a pyrolysis (EGA/PY-3030D, Fukushima-ken, Japan) gas chromatography–mass spectrometry (QP2010-Ultra, Kyoto, Japan) instrument (PY–GC/MS). The PY conditions were as follows: pyrolysis temperatures, 400 and 500 °C; pyrolysis time, 1 min; injection port temperature, 300 °C. The GC/MS conditions were as follows: capillary chromatographic column, ZB-5HT (30 mm × 0.25 mm × 0.25 μm); heating program: 50 °C, holding for 3 min, then heating to 300 °C at a rate of 10 K min−1, holding to 5 min; injection port temperature, 300 °C; split injection; split ratio 100:1; carrier gas (high-purity helium, 99.9999%) flow rate 1.0 mL min−1; collector temperature, 280 °C; ion source temperature, 250 °C; ion source scan mode, full scan (40–100 m/z).
By using these methods, the kinetic parameters of a solid-state reaction can be obtained without knowing the reaction mechanism.
In previous work [29–32], Kissinger method was widely used to determine the activation energies with the reaction process that occur under linear heating rate conditions. Although this method has some limitations, it is acceptable when an isoconversional method was used to back up the veracity of the Kissinger method . In addition, since the decomposition reaction process of the title compounds would be very complex, the values of E α of the title compounds obtained by the two isoconversional methods namely Kissinger–Akahira–Sunose  and Starink  method vary greatly and are disorder in the given range of α as 0.05–0.95. And many other types of kinetic methods  were tried to back up the veracity of the Kissinger method, but all of the results are unsatisfactorily. According to the literature [29, 36–39], an applicable method namely Ozawa–Doyle method was commonly used to back up the Kissinger method in the kinetic calculation of the energetic materials for its’ acceptable result.
In this equation, T P is the peak temperature of the DSC curve. The apparent activation energy (E) and pre-exponential factor (A) can be obtained from the slope −/(RT P ) and intercept ln(AR/E) respectively, of an ln (β/T P 2 ) versus 1/T P plot.
Results and discussion
The characteristic temperatures of the title compounds at different heating rates and the kinetic parameters
T 0 /°C
T e /°C
T P /°C
T 0 /°C
T e /°C
T P /°C
T 00 /°C
T e0 /°C
T P0 /°C
T 00 /°C
T e0 /°C
T P0 /°C
Data calculated by the Kissinger method
E K /kJ mol−1
ln(A K /s−1)
Linear correlation coefficient (r K )
Data calculated by the Ozawa–Doyle method
E O /kJ mol−1
Linear correlation coefficient (r O )
E a /kJ mol−1
From the thermogravimetric analysis results, we can calculate the kinetic parameters according to the model-free methods. The activation energy (E) and pre-exponential factor (A) were obtained using the Kissinger and Ozawa–Doyle methods.
From the original data of the exothermic peak temperature measured at five different heating rates of 5, 7, 10, 13, and 20 °C min−1 for 1, and 5, 7, 10, 15, and 20 °C min−1 for 2, the apparent activation energies E K and E O , the pre-exponential factors A K , and the linear coefficients r K and r O were determined, as shown in Table 2.
From Table 2, it can be seen that the apparent activation energies (E) for 1 and 2 obtained by the Kissinger method are very close to the values obtained by the Ozawa–Doyle method. The minor differences are assumed to stem from limitations of the method itself and errors in calculation. Moreover, the absolute values of the linear correlation coefficients (r) for 1 and 2 in Table 2 are close to 1, which indicates that the kinetic parameters were obtained with high accuracy.
Evidently, the values of apparent activation energy (E), extrapolated onset temperature (T e ), and critical temperature of thermal explosion (T b ) for 2 are consistently higher than those for 1, indicating greater thermodynamic stability of the former. Comparing the values of T b with those for other common energetic compounds: CL-20 (202.07 °C), HMX (267.43 °C), RDX (209.32 °C), NTO (265.53 °C), ENTO (227.44 °C), KNTO (226.32 °C) , ZTO (282.21 °C), ATO (299.64 °C), GZTO·H2O (237.74 °C) , and KZTO·H2O (275.08 °C) , the thermodynamic stability sequence of these compounds can be expressed as: 1 < CL-20 < RDX < KNTO ≈ ENTO < GZTO·H2O < NTO ≈ HMX < KZTO·H2O < ZTO ≈ 2 < ATO.
Thermal pyrolysis analysis
Pyrolysis–gas chromatography–mass spectrometry (PY–GC/MS) can be used to qualitatively analyze pyrolysis products. The pyrolysis chamber was heated to the preset temperature, then the sample was added, after 3 s, a fast heating process was performed and the pyrolysis process was carried out. Fragments were then separated by the GC column and their structures were identified by the MS system. For unknown compounds, one can obtain important information, such as their composition, microstructure, and so on. For known compounds, one can determine the pyrolysis products, and thereby infer the pyrolysis reaction pathways of the compound. This method has many advantages, including a very small injection volume, suitability for a broad range of samples, rapid analysis, and good reproducibility.
Because the molecules of 1 and 2 contain many C–N/N–N single and double bonds, their critical temperatures of thermal explosion (T b ) are below 300 °C. Hence, the explosion reaction must happen during the pyrolysis process, and the actual temperature at the reaction center may briefly reach thousands of degrees Celsius. In the pyrolysis of 1 and 2, following the initial decomposition of the reactive molecule, the pyrolysis products could undergo a multitude of collisions and numerous other reaction processes prior to collection and analysis by the GC/MS system. Hence, investigation of the rapid explosion reaction is a very difficult task, and the mechanistic interpretation inferred by us in this work should be placed in the context of the difficulty in truly isolating microscopic pathways of the explosion reaction.
Nevertheless, some fragments are yet unaccounted for, such as those with m/z 77 (Table 3, entries 8, 9, 11), m/z 154 (entries 21, 22), m/z 256 (entry 23), and m/z 175 (entry 24) for 1, and m/z 77 (Table 4, entry 8) for 2.
Experimental kinetic studies on the thermal decomposition processes of two typical nitrogen-rich energetic materials (1 and 2) were described, in which kinetic parameters, namely the apparent activation energy (E) and pre-exponential factor (lnA), were determined by the Kissinger and Ozawa–Doyle methods.
By the Kissinger method, values of E as 291.4 and 396.2 kJ mol−1 were obtained for 1 and 2, respectively, with lnA(s−1) values of 75.53 and 80.98, respectively. By the Ozawa–Doyle method, the values of E were 284.5 and 386.1 kJ mol−1 for 1 and 2, respectively, showing good agreement. The linear correlation coefficients (r) were close to 1, validating the results.
The critical temperatures of thermal explosion (T b ) were determined as 187.01 °C for 1 and 282.78 °C for 2. From the values of E, A, and T b , 2 is clearly more thermodynamically stable than 1. Critical temperatures of thermal explosion follow the sequence: 1 < CL-20 < RDX < KNTO ≈ ENTO < GZTO·H2O < NTO ≈ HMX < KZTO·H2O < ZTO ≈ 2 < ATO.
By PY–GC/MS, thermal pyrolyses of 1 and 2 at 400 and 500 °C generated a greater number of species. By analysis of the possible structures of the pyrolysis products, some conclusions about the pyrolysis pathways of 1 and 2 were drawn. The fragments detected by GC/MS following the pyrolyses of 1 and 2 were likely due to numerous secondary reactions, such as coupling, rearrangement, and addition or elimination of hydrogen atoms, of the smaller ion fragments derived from the explosion reactions (Additional file 1).
CJ, YL and SP conceived and designed the experiments. CJ and SZ performed the experiments. CJ, YL, SZ and TF analyzed the data. CJ completed the manuscript. All authors read and approved the final manuscript.
The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (21576026 and U153062).
The authors declare that they have no competing interests.
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The experiment data supporting the conclusions of this article are included within the article and its additional file.
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