The thermal decomposition of 2-methyloxetane and 3-methyloxetane has been studied between 660 and 760 K in the pressure range 0.01-3 kPa. In the pressure-independent range, rate coefficient expressions log(k1∞/s-1) = (14.53 ± 0.12) - (249.2 ± 2.2 kJ mol-1)/2.303RT and log(k2∞/s-1) = (15.67 ± 0.17) - (269.8 ± 3.3 kJ mol-1)/2.303RT were determined for 2-methyloxetane decomposition into C3H6 + HCHO (k1) and C2H4 + CH3CHO (k2), respectively, while for 3-methyloxetane decomposition into C3H6 + HCHO (k3) the following kinetic parameters were obtained: log(k3∞/s-1) = (15.38 ± 0.27) - (258.7 ± 3.7 kJ mol-1)/2.303RT. The pressure dependence of the homogeneous decomposition rate and the efficiency of the gas-phase collisional energy transfer have been studied at 743 K. A value of »δE«d = 1500 ± 300 cm-1 was extracted from the investigation of the pressure dependence of the two-channel decomposition of 2-methyloxetane. Finally, the efficiency of the surface-gas energy transfer has been studied by the 'variable encounter method' in the range 750-1100 K. At 750 K the average energy transferred per collision with the wall was determined to be 2600 cm-1 for both methyloxetanes; however, »δE'« decreased considerably with increasing temperature. The results on the collision efficiencies were discussed and compared with literature data for related molecules.
|Number of pages||5|
|Journal||Journal of the Chemical Society, Faraday Transactions|
|Publication status||Published - Dec 1 1990|
ASJC Scopus subject areas
- Physical and Theoretical Chemistry