摘要
单脉冲激波管实验方法研究了稀释于氩中的ＣＨ３Ｃｌ与Ｈ２的混合物，在高温下的裂解动力学，实验温度１０５Ｋ＜Ｔ＜１１７０Ｋ，压力０．５ＭＰａ＜Ｐ＜１ＭＰａ。实验结果表明符合以Ｈ·、ＣＨ３·和ＣＨ２Ｃｌ·自由基为活化中心的链反应机制。始发反应ＣＨ３Ｃｌ ＣＨ３·＋Ｃｌ·处于递降区，反应速率常数ｋ１＝１０×１０１５ｅｘｐ（－４１１００／）ｓ－１，在Ｐ＝１ＭＰａ；ｋ１＝６．６ｘ１０１４ｅｘｐ（－４０７００／Ｔ）ｓ－１，在Ｐ＝０．５ＭＰａ。确定了氢攻击ＣＨ３Ｃｌ的反应有两个通道，即 和分支比 ＝２．８，及Ｋ３＝９．７ｘ１０１２ｅｘｐ（－４８６０／Ｔ）ｃｍ３ｍｏｌ－１ｓ－１。产物Ｃ２Ｈ４是由一氯甲基与氢原子复合生成亚甲基 后续反应ＣＨ２：＋ＣＨ３Ｃｌ Ｃ２Ｈ４＋ＨＣｌ给出，其速率常数ｋ５＝８．２ｘ１０１５Ｔ－０．６３ｅｘｐ（－２５４／Ｔ）ｃｍ３ｍｏｌ－１ｓ－１。
The mixtures of CH3Cl and H2 diluted in argon are shocked in a single pulse shocktube and the kinetics of the decomposition of CH3Cl is studied at the temperature range1050K< T< 1170 K, pressure range 0.5 MPa <P<1 MPa. To interpret the experimental results,a chain reaction scheme is proposed and the following conclusions are leaded. The branchingratio of the reactions H +CH3Cl and is determined as k3/k3 = 2.8, With the rate constant. k3= 9.7 x 1012exp(-4860/T)cm3mol-1s-1. The initiation reaction CH3Cl .is in the fall off region, near the high pressure limit, andk1=1 .0 x 1015exp (-41100/T)s-1, P= 1 MPa and k1= 6.6 × 1014exp (-40700/ T)s-1, P=0.5 MPaare determined. The mechanism of the production of C2H4 is revealed as reaction of CH2ClHCl followed by CH2:+CH3Cl C2H4+HCl, with the rate constantk5=8.2 x 1015 exp (-254/ 7) cm3 mol-1 s-1.
基金
国家自然科学基金
