(二硝基吡唑基)偶氮氧呋喃烷的热分解动力学及分解机理

IF 1.6 4区 化学 Q4 CHEMISTRY, PHYSICAL
Valery P. Sinditskii, Ludmila Ya. Melnikova, Anastasia D. Smirnova, Nikolay V. Yudin, Alexei A. Konnov, Igor L. Dalinger, Michael S. Klenov
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引用次数: 0

摘要

本文采用DSC、热重分析、等温热重分析和测压等方法,详细研究了氮氧基二硝基吡唑和呋喃唑衍生物的分解,这是氮氧基与吡唑环氮偶联的第一个例子。研究表明,偶氮基化合物的降解始于偶氮基N(O)原子与呋喃氮循环之间的键断裂。发现在分解产物去除的条件下,这一阶段可以发生无放热或放热无明显峰值。偶氮化合物分解初期的热效应不明显,这使得用标准DSC方法很难确定真正的动力学参数,因为观察到的热效应实际上是由中间体分解引起的。同时,封闭条件下的分解可使分解速率常数提高10倍以上。根据所获得的动力学数据和对分解产物的分析,提出了偶氮基化合物分解的可能机理。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Thermal Decomposition Kinetics and Decomposition Mechanism of (Dinitropyrazolyl)Azoxyfurazanes

The decomposition of azoxy derivatives of dinitropyrazole and furazan, the first example in which an azoxy group is coupled to a pyrazole ring nitrogen, has been studied in detail using DSC, TGA, isothermal TGA, and manometry methods. The studies showed that the degradation of azoxy compounds starts with the cleavage of the bond between the N(O) atom of the azoxy group and the furazan cycle. It was found that under conditions of decomposition product removal, this stage can occur without heat release or with heat release without a pronounced peak. The insignificant heat effect of the initial decomposition stage of azoxy compounds makes it difficult to determine the true kinetic parameters using the standard DSC method, as the observed heat effect is actually due to the decomposition of intermediates. At the same time, decomposition under closed conditions can increase the decomposition rate constants by a factor of 10 or more. A possible mechanism for the decomposition of azoxy compounds has been proposed based on the kinetic data obtained and the analysis of the decomposition products.

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来源期刊
CiteScore
3.30
自引率
6.70%
发文量
74
审稿时长
3 months
期刊介绍: As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.
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