Kinetics of decomposition of 1,1-diamino-2,2-dinitroethylene (FOX-7). 6. The induction period at the early stages of the reaction in the solid state

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Abstract

The kinetics of thermal decomposition of FOX-7 compound at 155 °C under semi-open conditions in vessels with a volume of V = 0.8–0.9 cm3 in an air atmosphere and the degree of filling of the vessel with substances m/V = 0.03–0.72 g/cm3 has been studied by gravimetric method. It was found that at the largest m/V, an induction period is observed at the early stages of the reaction, during which the rate of mass loss of the sample is ten times less than the rate of decomposition of FOX-7 in the solid phase. With a decrease in m/V, the induction period is shortened and at m/ V = 0.04 g/cm3 disappears altogether. The appearance of the induction period is due to the fact that nitronic acid, which is the only product of the first stage of decomposition of FOX-7, is well adsorbed on the surface of FOX-7 crystals. At the same time, it almost completely loses its reactivity. As a result, until the end of the adsorption process, the decomposition of FOX-7 proceeds without the formation of gaseous products, and the reaction rate is not fixed by the gravimetric method suitable for studying the kinetics of the reaction at the early stages of decomposition FOX-7.

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About the authors

G. M. Nazin

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: akazakov@icp.ac.ru
Russian Federation, Chernogolovka

A. I. Kazakov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: akazakov@icp.ac.ru
Russian Federation, Chernogolovka

A. V. Nabatova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: akazakov@icp.ac.ru
Russian Federation, Chernogolovka

N. N. Volkova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: akazakov@icp.ac.ru
Russian Federation, Chernogolovka

G. V. Shilov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences

Email: akazakov@icp.ac.ru
Russian Federation, Chernogolovka

References

  1. G.M. Nazin, V.V. Dubikhin, T.K. Goncharov, A.I. Kazakov, A.V. Nabatova, A.V. Shastin, Russ. J. Phys. Chem. B 15, 483 (2021). https://doi.org/10.1134/S1990793121030283
  2. G.M. Khrapkovskii, A.G. Shamov, E.V. Nikolaeva, D.V. Chachkov. Russ. Chem. Rev. 78 , 903 (2009). https://doi.org/10.1070/RC2009v078n10ABEH004053
  3. Nazin G.M., Kazakov A.I., Larikova T.S., Nabatova A.V., Volkova N.N., Kinetics of decomposition of 1,1-dia mino-2,2-dinitroethylene (FOX-7). 5. Vapor pressure and reaction in the gas phase, Russ. J. Phys. Chem. B 18, 663 (2024). https://doi.org/10.1134/S1990793124700118
  4. G.M. Nazin, V.V. Dubikhin, T.K. Goncharov, A.I. Kaza kov, A.V. Nabatova, A.V. Shastin, Russ. J. Phys. Chem. B 15, 604 (2021). https://doi.org/10.1134/S1990793121040059
  5. Hodge E.B. // J. Amer. Chem. Soc. 73, 2341 (1951).
  6. The Chemistry of the Nitro and Nitroso Groups, Ed. by Feuer H., (Interscience Publishers, New York–London–Sidney–Toronto, 1969, Part 1).

Supplementary files

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2. Fig. 1. Scheme of the initial stages of decomposition of the FOX-7 compound.

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3. Fig. 2. Kinetic curves of FOX-7 decomposition at 155 °C. The numbers on the curves correspond to the experiment numbers from Table 1.

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4. Fig. 3. Kinetic curve of FOX-7 decomposition at a temperature of 170 °C, constructed based on the results of experiment No. 6 and the data in Table 1; data from experiment No. 7 – □, data from experiment No. 8 – ○.

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