| 纳米结晶体Ni0.5Zn0.5Fe2O4对高氯酸铵热行为及分解反应动力学的影响(英文) |
| Effect of Nanocrystal Ni0.5Zn0.5Fe2O4 on Thermal Behavior and Decomposition Reaction Kinetics of Ammonium Perchlorate |
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| 摘要: 采用差示扫描量热法(DSC)、热重和微分热重(TG-DTG)及固相原位反应池/快速扫描傅立叶变换红外联用技术(hyphenated in situ thermolysis/RSFTIR)研究了纳米结晶体Ni0.5Zn0.5Fe2O4与高氯酸铵(AP)组成的混合物的热行为和分解反应动力学。结果表明：Ni0.5Zn0.5Fe2O4使得AP的低、高温分解放热峰温分别提前17.44 K和27.74 K，并使得对应的分解热分别增加3.7 J·g-1和193.7 J·g-1。Ni0.5Zn0.5Fe2O4并不影响AP的晶转温度和晶转热。Ni0.5Zn0.5Fe2O4使得AP的TG曲线出现3个阶段，并使得后2个失重阶段的初始和终止温度都有所提前。凝聚相分解产物分析表明Ni0.5Zn0.5Fe2O4加速了凝聚相AP的分解及氨气的释放。含Ni0.5Zn0.5Fe2O4的AP的高温分解反应的动力学参数Ea=238.88 kJ·mol-1，A=1018.59 s-1，动力学方程可表示为dα/dt=1018.99(1-α)[-ln(1-α)]3/5e-2.87×104T。始点温度(Te)和峰顶温度(Tp)计算得出AP的热爆炸临界温度值分别为:574.83 K和595.41 K。分解反应的活化熵(ΔS≠)、活化焓(ΔH≠)和活化能(ΔG≠)分别为:109.61 J·mol-1·K-1、236.49 kJ·mol-1及172.58 kJ·mol-1。 |
| 关键词: 纳米结晶体 Ni0.5Zn0.5Fe2O4 高氯酸铵(AP) 热行为 非等温反应动力学 |
| 基金项目: |
| Abstract: The thermal behavior and non-isothermal decomposition reaction kinetics of the mixture of the nanocrystal Ni0.5Zn0.5Fe2O4 and ammonium perchlorate (AP) were investigated by differential scanning calorimetry (DSC), thermogravimetry and differential thermogravimetry (TG-DTG), and the hyphenated technique of in situ thermolysis cell with rapid-scan Fourier transform infrared spectroscopy (in situ thermolysis/RSFTIR). The results show that Ni0.5Zn0.5Fe2O4 can decrease the low-temperature and the high-temperature exothermic peak temperatures of AP by 17.44 K and 27.74 K, respectively, and increase the decomposition heats of the two exothermic peaks by 3.7 J·g-1 and 193.7 J·g-1, respectively. Ni0.5Zn0.5Fe2O4 does not affect the crystal transformation temperature and heat of AP. Ni0.5Zn0.5Fe2O4 makes AP shown three mass-loss processes, and it can decrease the initial and terminated temperatures of the last two mass-loss stages. The condensed phase decomposition product analysis shows that Ni0.5Zn0.5Fe2O4 accelerates the decomposition of condensed AP and the release of the gaseous NH3. The kinetic parameters Ea=238.88 kJ·mol-1, A=1018.59 s-1, and the kinetic equation of the high-temperature decomposition reaction of Ni0.5Zn0.5Fe2O4/AP can be described as: dα/dt=1018.99(1-α)[-ln(1-α)]3/5e-2.87×104T. The corresponding critical temperatures of thermal explosion (Tbe and Tbp) corresponding to β→0 are 574.83 K and 595.41 K, respectively. The entropy of activation (ΔS≠), enthalpy of activation (ΔH≠), and free energy of activation (ΔG≠) of the decomposition reaction are 109.61 J·mol-1·K-1, 236.49 kJ·mol-1, and 172.58 kJ·mol-1, respectively. |
| Keywords: Nanocrystal Ni0.5Zn0.5Fe2O4 ammonium perchlorate (AP) thermal behavior non-isothermal reaction kinetics |
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| 仪建华,赵凤起,胡荣祖,Gurdip Singh.纳米结晶体Ni0.5Zn0.5Fe2O4对高氯酸铵热行为及分解反应动力学的影响(英文)[J].无机化学学报,2008,24(2):246-252. |
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