三唑含能离子盐的热化学性质和热动力学行为  

Thermochemical properties and thermokinetic behavior of energetic triazole ionic salts

作　　者：赵凤起[1,2] 薛亮[1,2,3] 邢晓玲[1,2] 胡荣祖[1,2] 周智明[4] 高红旭[1,2] 仪建华[1,2] 徐司雨[1,2] 裴庆[1,2] 

机构地区：[1]火炸药燃烧国防科技重点实验室 [2]西安近代化学研究所,西安710065 [3]陕西师范大学化学与材料科学学院,西安710062 [4]北京理工大学环境化工学院,北京100081

出　　处：《中国科学：化学》2010年第9期1430-1443,共14页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(20573098);火炸药燃烧国防科技重点实验室基金(9140C3503030805)资助

摘　　要：用微量热技术测量1,2,4-三唑硝酸盐(1a)、1,2,3-三唑硝酸盐(1b)、3,4,5-三氨基-1,2,4-三唑硝酸盐(2a)、3,4,5-三氨基-1,2,4-三唑二硝酰胺盐(2b)4种三唑类含能离子盐的溶解过程热效应、比热容(283K<T<353K)及非等温条件下的热分解过程.用处理实验数据和理论计算方法获得了1a、1b、2a、2b溶解过程的热化学方程式、微分溶解焓、摩尔溶解焓、动力学方程式、活化能、指前因子、283～353K温区内比热容随温度变化的线性关系式、标准摩尔热容CpΘ,m和285～353K温区以298.15K为基准的焓、熵和Gibbs自由能函数值.计算了热分解反应的动力学参数、热力学参数以及评估了1a、1b、2a、2b对热的抵抗能力.得到了化合物性质与分子结构之间内在关系的信息.The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate （1a）,1,2,3-triazolium nitrate （1b）,3,4,5-triamino-1,2,4-triazolium nitrate （2a）,3,4,5-triamino-1,2,4-triazolium dinitramide （2b） were measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution （Δ dif HmΘ）,standard molar enthalpies of dissolution （Δ diss HmΘ）,apparent activation energy （E）,pre-exponential constant （A）,kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 K to 353 K,standard molar heat capacity （CpΘ,m） and enthalpy change,entropy change and Gibbs free energy change at 283？353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion （Tb）,self-accelerating decomposition temperature （TSADT） and adiabatic time-to-explosion （t） of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.

关 键 词：含能三唑离子盐 热化学性质 热动力学行为 热安全性 

分 类 号：O626.26[理学—有机化学]