高氯酸碳酰肼钴、高氯酸碳酰肼镍快速热分解反应动力学

利用温度跃升傅立叶变换红外原位分析技术(T-jump/FTIR)对高氯酸碳酰肼钴和高氯酸碳酰肼镍的快速热分解反应进行了研究. 研究表明, 目标化合物快速热分解逸出的主要气相产物是CO2, H2O, HCN, HNCO和HONO. 借助快速升温过程中Pt金属丝的控制电压变化曲线得到剧烈放热峰的诱导出现时间tx, 利用tx值计算了两种目标化合物的快速热分解动力学参数. 在0.1 MPa氩气气氛, 613～653 K的实验温度范围内, 高氯酸碳酰肼钴的活化能Ea=39.42 kJ?mol?1, lnA=5.93; 在0.1 MPa氩气气氛, 618～678 K的实验温度范围内, 高氯酸碳酰肼镍的活化能Ea=60.44 kJ?mol?1, lnA=9.40.

Kinetics of Flash Pyrolysis of [Co(CHZ)3](ClO4)2 and [Ni(CHZ)3](ClO4)2

T-jump/FTIR spectroscopy was used to study thermal decomposition of energetic material Co(CHZ)3](ClO4)2and Ni(CHZ)3](ClO4)2 in thin film with rapid heating rate. During the exothermic decomposition process, the major gas products were identified as CO2, H2O, HCN, HNCO, and HONO. Time-to-exotherm (tx) kinetics method derived from the control voltage trace of T-jump/FTIR spectroscopy was introduced to resolve kinetics of the exothermic decomposition reaction of flash pyrolysis of the title compounds. In the temperature range of 613～653 K under 0.1 MPa Ar atmosphere the Arrhenius activation energy of the exothermic decomposition reaction of Co(CHZ)3](ClO4)2 was determined to be Ea=39.42 kJ·mol-1 and InA=5.93. The Arrhenius activation energy of Ni(CHZ)3](ClO4)2 was determined to be Ea=60.44 kJ·mol-1 and lnA=9.40 in the temperature range of 618～678 K under 0.1 MPa Ar atmosphere.