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

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Abstract
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 temperature range 280 to 360° K by continuous optical absorption measurements at 2537 Å. The technique was tested by measuring the rate constants k1 and k2 of the reactions (1) NO + O3 → NO2 + O2 and (2) NO2 + O3 rarr; NO3 + O2 which are known from the literature. The results for NO, NO2, C2H4, C3H6, 2‐butene (mixture of the isomers), 1,3→butadiene, isobutene, and 1,1 ‐difluoro‐ethylene are 1.7 × 10−1 4 (290°K), 3.24 × 10−17 (289°K), 1.2 × 10−1 4 exp (–4.95 ± 0.20/RT), 1.1 × 10−1 4 exp (–3.91 ± 0.20/RT), 0.94 × 10−1 4 exp ( –2.28 ± 0.15/RT), 5.45 ± 10−1 4 exp ( –5.33 ± 0.20/RT), 1.8 ×10−17 (283°K), and 8 × 10−20 cm3/molecule ·s(290°K). Productformation 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.

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