Kinetics of Decomposition of 1,1-Diamino-2,2-dinitroethylene (FOX-7). 6. The Induction Period in the Early Stages of a Reaction in the Solid State

IF 1.4 4区化学 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL

Russian Journal of Physical Chemistry B Pub Date : 2024-09-11 DOI:10.1134/s1990793124700350

G. M. Nazin, A. I. Kazakov, A. V. Nabatova, N. N. Volkova, G. V. Shilov

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Abstract

The kinetics of the thermal decomposition of the FOX-7 compound at 155°C under semiopen 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 the gravimetric method. It is found that at the largest m/V, an induction period is observed in the early stages of the reaction, during which the rate of mass loss of the sample is lower by a factor of ten 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 it 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 of FOX-7.

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1,1-Diamino-2,2-dinitroethylene (FOX-7) 的分解动力学。6.固态反应早期阶段的诱导期

摘要通过重量法研究了 FOX-7 化合物在 155°C 半开放条件下，在容积为 V = 0.8-0.9 cm3 的容器中，在空气环境和容器中物质填充度 m/V = 0.03-0.72 g/cm3 的条件下的热分解动力学。研究发现，当 m/V 最大时，反应初期会出现一个诱导期，在此期间，样品的质量损失率比 FOX-7 在固相中的分解率低 10 倍。随着 m/V 的减小，诱导期缩短，当 m/V = 0.04 g/cm3 时，诱导期完全消失。诱导期的出现是由于硝酸（FOX-7 第一阶段分解的唯一产物）很好地吸附在 FOX-7 晶体表面。同时，它几乎完全失去了反应活性。因此，直到吸附过程结束，FOX-7 的分解过程一直在进行，没有形成气态产物，而适合研究 FOX-7 分解早期阶段反应动力学的重量法无法固定反应速率。

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来源期刊

Russian Journal of Physical Chemistry B 化学-物理：原子、分子和化学物理

CiteScore

2.20

自引率

71.40%

发文量

106

审稿时长

4-8 weeks

期刊介绍： Russian Journal of Physical Chemistry B: Focus on Physics is a journal that publishes studies in the following areas: elementary physical and chemical processes; structure of chemical compounds, reactivity, effect of external field and environment on chemical transformations; molecular dynamics and molecular organization; dynamics and kinetics of photoand radiation-induced processes; mechanism of chemical reactions in gas and condensed phases and at interfaces; chain and thermal processes of ignition, combustion and detonation in gases, two-phase and condensed systems; shock waves; new physical methods of examining chemical reactions; and biological processes in chemical physics.