基于质谱的六硝基六氮杂异伍兹烷热分解动力学

采用低能电子轰击质谱研究了六硝基六氮杂异伍兹烷(HNIW)的裂解过程, 建立了质谱中离子强度曲线的非等温动力学处理方法, 根据产物离子的Arrhenius曲线解释了HNIW热分解的机理. 结果表明, HNIW质谱裂解的表观活化能为145.1 kJ·mol-1. 在130-150 ℃范围内, HNIW质谱的离子产物主要是电子轰击产生的, 其活化能在28-41 kJ·mol-1之间; 在213-228 ℃范围内, 离子主要是热分解产生的, 其活化能在143-179 kJ·mol-1之间. HNIW在213-228 ℃的热分解动力学参数存在良好的动力学补偿效应, 补偿效应公式为lnA=0.252Ea-0.645. HNIW 热分解的主要反应为HNIW.438→6NO2+2HCN+HNIW.108, HNIW.438→6NO2+3HCN+HNIW.81, HNIW.438→6NO2+4HCN+HNIW.54.

Thermal Decomposition Kinetics of Hexanitrohexaazaisowurtzitane by Mass Spectrometry

Thermal decomposition of hexanitrohexaazaisowurtzitane (HNIW)was studied bymass spectroscopy (MS) with low impacting electron energy. Non-isothermal kinetics treating method for ion curves in mass spectroscopy was established. The mechanism of HNIW thermal decomposition was analyzed according to the Arrhenius curves of ion products. The results showed that the apparent activation energy of the HNIW thermal decomposition was 145.1 kJ·mol-1. Between 130 and 150 ℃, ion products are mainly produced by electron impact, and activation energy is between 28 and 41 kJ·mol -1. Between 213 and 228 ℃, ion products are mainly produced by thermal decomposition, and activation energy is between 143 and 179 kJ·mol-1. The kinetic compensation effect occurs in thermal decomposition of HNIWbetween 213 and 228 ℃, and the compensation effect equation is lnA=0.252Ea-0.645. The main reactions of HNIWthermal decomposition are as HNIW.438→6NO2+2HCN+HNIW.108, HNIW.438→6NO2+3HCN+HNIW.81, HNIW.438→6NO2+4HCN+HNIW.54.