Reaction between ozone and allene in the gas phase

✍ Scribed by Frina S. Toby; Sidney Toby

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 490 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060311

✦ Synopsis

The kinetics of the reaction between ozone and allene (A) were studied in the range of 226 to 325°K in the gas phase. Initial O3 pressures varied from 0.01 to 0.7 torr and allene pressures varied from 0.05 to 6 torr. At the higher initial 0 3 pressures the most important product was 0 2 followed by CO, H20, Cot, and CTH,. Oxygen balances averaging about llOyo were obtained, which implies that no important oxygenated products were missed. However, carbon balances were only about 5oy0 and hydrogen balances were even less, so that unidentified hydrocarbons were presumably formed. The

rate law found was --d[O3]/dt = kl[03][A] + k 2 a [ 0 3 ] 2 [ A ] / [ 0 3 ] ~

where log kl(M-'sec-') = 6.0 & 0.7 -(5500 =t 1000)/2.30RTand log kt,(M-lsec-l) = 6.9 f 0.7 -(6200 +800/ 2.30RT. A mechanism is proposed which accounts for the rate law and the observed stoichiometry of 0 2 formed-03 used. This involves a heterogeneous catalyzed decomposition of 0 3 . The rate constant k , is identified with the primary addition reaction A + 0 3 4 AO3, and this rate constant is compared with those from other 0 3 addition reactions.