T-Jump/FTIR技术研究3,4-二硝基呋咱基氧化呋咱快速热裂解

Investigation on the Flash Thermolysis of 3,4-Dinitrofurazan-furoxan by T-Jump/FTIR Spectroscopy

采用温度快速跃迁原位池与快速扫描傅里叶变换红外联用(T-Jump/FTIR)技术在0.1-0.4MPa压强范围内研究了3,4-二硝基呋咱基氧化呋咱(DNTF)的快速热裂解.试验是以1000℃·s-1的升温速率在800和1000℃的温度下进行,用快速扫描傅里叶变换红外光谱实时跟踪分析DNTF裂解的气相产物.结果表明,DNTF快速热裂解的主要产物CO、CO2、NO和NO2的相对摩尔浓度c*与温度和压强有关,通过分析相对摩尔浓度比(c*NO/c*NO2)随温度和压强的变化,揭示了DNTF中碳硝基C—NO2存在均裂生成NO2和异构化生成NO两条竞争分解的可能途径,同时压强可能抑制呋咱环和氧化呋咱环生成NO的可能性.压强升高使c*CO和c*CO2升高,而使c*CO/c*CO2下降,证明DNTF的分解中存在非均相的气相/凝聚相反应和均相的气相产物间反应的二次或三次过程.

The fast thermolysis of 3,4-dinitrofurazanfuroxan （DNTF） at 0.1-0.4 MPa was investigated by temperaturejump Fourier transform infrared （T-jump/FTIR） spectroscopy.All tests were carried out using a heating rate of 1000 ℃·s^-1 at 800 and 1000 ℃.Structures and concentrations of the gaseous products were obtained in situ and in real time by fast scanning FTIR.Results showed that the relative molar concentrations c of the main gaseous products （CO,CO2,NO and NO2） that were released by the thermolysis of DNTF were related to pressure and temperature.The relative molar concentration ratios of cNO/cNO2changes as the temperature and pressure change.These results reveal that the two competitive reactions of C—NO2 homolysis （to form NO2） and isomerization （to form NO） may occur during the fast thermolysis of DNTF.NO formation from the cracking of furazan or furoxan rings may be limited by pressure.Heterogeneous gas/condensed phase and homogeneous gas phase reactions may occur in the secondary and tertiary class reactions of the fast thermolysis of DNTF because the relative molar concentrations of cCO and cCO2increase and the relative molar concentration ratios of cCO /cCO2decrease with increasing pressure.