Ozone–olefin reactions in the gas phase 1. Rate constants and activation energies

✍ Scribed by K. H. Becker; U. Schurath; H. Seitz

• Publisher: John Wiley and Sons
• Year: 1974
• Tongue: English
• Weight: 761 KB
• Volume: 6
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550060509

✦ Synopsis

Reactions of ozone with simple olefins have been studied between 6 and 800 mtorr total pressure in a 220-m3 reactor. Rate constants for the removal of ozone by an excess of olefin in the presence of 150 mtorr oxygen were determined over the iemperature range 280 to 360" K by continuous optical absorption measurements at 2537 A. The technique was tested by measuring the rate constants kl and k 2 of the reactions ( I ) NO + 0 3 -+ NO2 + 0 2 and (2) NO2 + 0 3 + NO3 + O 2 which are known from the literature. The results for NO, NO*, C2H4, C3H6, 2-butene (mixture of the isomers), 1,3-butadiene, isobutene, and l,l-difluoro-ethylene are 1.7 X (290°K), 3.24 X 1O-l' (289"K), 1.2 X exp (-4.95 &0.20/RT), 1.1 X 10-14exp (-3.91 +0.20/RT),0.94 X 10-14exp (-2.28 + O.l5/RT), 5.45 X exp (-5.33 i 0.20/RT), 1.8 X lo-" (283OK), and 8 X lo-'* cm3/molecule .s(290°K). Product formation from the ozone-propylene reaction was studied by a mass spectrometric technique. The stoichiometry of the reaction is near unity in the presence of molecular oxygen.