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使用加速量热仪研究硝酸正丙酯(NPN)、硝酸异丙酯(IPN)和硝酸异辛酯(EHN)的热分解过程.分析了在绝热条件下热分解反应动力学,根据实验数据计算出表现活化能、指前因子和反应热等参数.根据NPN、IPN和EHN热分解的起始温度和反应热数据,给出了三种硝酸酯在75℃时的反应风险指数,分析得到三种物质的热失稳风险度.分别在B3LYP/6-31+G(2df,2p)和B3P86/6-3l+G(2df,2p)的理论水平下,计算得到NPN、IPN和EHN的O—NO_2键离解能(BDE).由NPN、IPN和EHN的O—NO_2键离解能在很大程度上符合由加速量热仪测试得到的活化能,推知三种硝酸酯的热分解反应只是单分子O—NO_2键的均裂反应.
The thermal decomposition process of n-propyl nitrate (NPN), isopropyl nitrate (IPN) and isooctyl nitrate (EHN) was studied using an accelerated calorimeter.The kinetics of thermal decomposition under adiabatic conditions was analyzed and calculated based on experimental data Exponential activation energy, exponential factor and heat of reaction, etc. According to the onset temperature and reaction heat data of thermal decomposition of NPN, IPN and EHN, the reaction risk index of three nitrates at 75 ℃ is given. The risk of thermal instability of the species was calculated by the theoretical calculations of B3LYP / 6-31 + G (2df, 2p) and B3P86 / 6-3l + G (2df, 2p) -NO 2 bond dissociation energy (BDE). The dissociation of O-NO 2 bonds by NPN, IPN and EHN can largely accord with the activation energy measured by accelerated calorimeter. It is deduced that the thermal decomposition reaction of the three nitrates is only a single Molecular O-NO_2 bond cleavage reaction.