四水合5,5'-联四唑-1,1'-二氧二钠盐的热行为与热分解动力学

Thermal Behavior and Thermal Decomposition Kinetics of Disodium 5,5'-Bistetrazole-1,1'-Diolate Tetrahydrate

采用差热-热重分析仪(TDA-TG),加速绝热量热仪(ARC),热重-质谱分析仪(TG-MS)测定了四水合5,5'-联四唑-1,1'-二氧二钠盐([Na_2(BTO)(H_2O)_4])的热分解过程,获得了[Na_2(BTO)(H_2O)_4]非等温条件下的动力学参数及热分解机理和绝热条件下分解的温度、压力、温升速率等随时间的变化曲线以及温升速率、分解压力随温度的变化曲线。结果表明:[Na_2(BTO)(H_2O)_4]的分解过程包含配位水脱除和分解、放热三个主要阶段,第一阶段配位水脱除和第二阶段配位水脱除的的机理函数分别为dα/d T=10^(23.33)/βexp(-2.23×10~4/T)(1-α)[-ln(1-α)]^(-1/2)和dα/d T=10^(36.96)/βexp(-3.74×10~4/T)(1-α)[-ln(1-α)]-1,放热分解阶段的机理函数为F2/D1(二级反应和一维扩散)的组合;修正后绝热分解过程的初始放热温度为305.82℃,绝热温升为1 887.3℃,体系最高放热温度和最大压力分别为330.93℃和12.618 bar;TG-MS研究显示在热分解峰温处检测到荷质比为m/z=14(CH_2^+)、m/z=30(NO^+)、m/z=28(N_2^+)、m/z=29(CHO^+)、m/z=44(N_2O^+)、m/z=27(HCN+)、m/z=2(H_2^+)的粒子流。

To explore the stability of disodium 5,5＇-bistetrazole-1,1＇-diolate tetrahydrate [Na_2（BTO）（H_2O）_4],the decomposition process of [Na_2（BTO）（H_2O）_4] was studied by differential thermal analysis-thermal gravity（TDA-TG）, accelerating rate calorimeter（ARC） and thermal gravity-mass spectrometer analysis（TG/MS）.The thermal decomposition mechanism and kinetics parameters of[Na_2（BTO）（H_2O）_4]under non-isothermal and the decomposition temperature,pressure and temperaturerise rate versus time curves,and pressure and temperature rise rate versus temperature curves were obtained.Results show that thermal decomposition process of [Na_2（BTO）（H_2O）_4]can be divided into three stages,coordination water removal and exothermic decomposition.The kinetic equations for the first stage coordination water removal and the second stage coordination water removal of [Na_2（BTO）（H_2O）_4]may be expressed asddα/d T=10^（23.33）/βexp（-2.23×10~4/T）（1-α）[-ln（1-α）]^（-1/2） and dα/d T=10^（36.96）/βexp（-3.74×10~4/T）（1-α）[-ln（1-α）]-1.The most probable mechanism function of the thermal decomposition of [Na_2（BTO）（H_2O）_4] was composed by F2/D1（two stage reaction and one dimensional diffusion）.The revised initial exothermic temperature for adiabatic thermal decomposition process of [Na_2（BTO）（H_2O）_4] was 305.82 ℃,adiabatic temperature rise 1887.3 ℃,the maximum exothermic temperature and pressure of the reaction system were 330.93 ℃ and 12.618 bar.The thermolysis performance of [Na_2（BTO）（H_2O）_4] was studied by thermal gravity/mass spectrometer analysis（TG/MS）.Result show m/z=14（CH_2~＋）,m/z=30（NO~＋）,m/z=28（N_2~＋）,m/z=29（CHO~＋）,m/z=44（N_2O~＋）,m/z=27（HCN＋）,m/z=2（H_2~＋） was detected in the temperature of decomposition