Abstract:
The mixtures of CH
3Cl and H
2 diluted in argon are shocked in a single pulse shock tube and the kinetics of the decomposition of CH
3Cl is studied at the temperature range 1050K<
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 branching ratio of the reactions \mathrmH \cdot+\mathrmCH_3 \mathrmCl \xrightarrowk_3 \mathrmHCl+\mathrmCH_3 \cdot and \mathrmH \cdot+\mathrmCH_3 \mathrmCl \xrightarrowk_3^\prime \mathrmH_2+\mathrmCH_2 \mathrmCl \cdot is determined as
k3/
k3’=2.8,With the rate constant.
k3=9.7×10
12exp(-4860/
T)cm
3mol
-1s
-1.The initiation reaction \mathrmCH_3 \mathrmCl \xrightarrowk_1 \mathrmCH_3 \cdot+\mathrmCl \cdot.is in the fall off region,near the high pressure limit,and
k1=1.0 × 10
15exp (-41100/
T)s
-1,
P=1 MPa and
k1=6.6 × 10
14exp (-40700/
T)s
-1,
P=0.5 MPa are determined.The mechanism of the production of C
2H
4 is revealed as reaction of CH
2Cl·+\mathrmH \cdot \xrightarrowk_5 \mathrmCH_2:+\mathrmHCl followed by \mathrmCH_2:+\mathrmCH_3 \mathrmCl \xrightarrow\text Fast \mathrmC_2 \mathrmH_4+\mathrmHCl,with the rate constant
k5=8.2×10
15 T0.63exp (-254/
T)cm
3mol
-1s
-1.